Compounds for electronic devices

ABSTRACT

The present invention relates to compounds of the formula (1) or (2) and to the use thereof in electronic devices, and to electronic devices which comprise these compounds. The invention furthermore relates to the preparation of the compounds of the formula (1) or (2) and to formulations comprising one or more compounds of the formula (1) or (2).

The present invention relates to compounds of the formula (1) or (2) andto the use thereof in electronic devices, and to electronic deviceswhich comprise these compounds. The invention furthermore relates to thepreparation of the compounds of the formula (1) or (2) and toformulations comprising one or more compounds of the formula (1) or (2).

The compounds of the formula (1) or (2) are used in accordance with theinvention in electronic devices, preferably in organicelectroluminescent devices (OLEDs). The general structure of thesedevices is described, for example, in U.S. Pat. No. 4,539,507, U.S. Pat.No. 5,151,629, EP 0676461 and WO 98/27136.

Hole-transport and -injection materials which are known from the priorart for organic electroluminescent devices are, inter alia, arylaminecompounds. Materials of this type based on an indenofluorene skeletonare disclosed, for example, in WO 2006/100896 and WO 2006/122630.

However, the hole-transport materials known from the prior artfrequently have low electron stability, which reduces the lifetime ofelectronic devices comprising these compounds. Overall, furtherimprovements are desirable with respect to the efficiency of fluorescentorganic electroluminescent devices and the lifetime, especially in thecase of blue-fluorescent devices. There is also potential forimprovement in the operating voltage of the electronic devices.

There is therefore a demand for alternative compounds which can be used,inter alia, as hole-transport materials in organic electroluminescentdevices and which preferably effect an improvement in theabove-mentioned performance data of the devices.

Matrix materials which are known from the prior art for phosphorescentdopants are, inter alia, carbazole derivatives, for examplebis(carbazolyl)-biphenyl. The use of ketones (WO 2004/093207), phosphineoxides and sulfones (WO 2005/003253) as matrix materials forphosphorescent dopants is furthermore known. Metal complexes, forexample BAlq or zinc(II) bis[2-(2-benzothiazolyl)phenolate], are alsoused as matrix materials for phosphorescent dopants.

However, there continues to be a demand for alternative matrix materialsfor phosphorescent dopants, in particular those which effect animprovement in the performance data of the electronic devices.

Also of particular interest is the provision of alternative materials asmatrix components of mixed-matrix systems. A mixed-matrix system in thesense of this application is taken to mean a system in which two or moredifferent matrix compounds are used as a mixture together with one (ormore) dopant compounds in an emitting layer. These systems are, inparticular, of interest in the case of phosphorescent organicelectroluminescent devices. For more detailed information, reference ismade to the application WO 2010/108579.

Compounds known from the prior art which may be mentioned as matrixcomponents in mixed-matrix systems are, inter alia, CBP(biscarbazolylbiphenyl) and TCTA (triscarbazolyltriphenylamine) (firstcomponent). Suitable as the second component are compounds such as, forexample, benzophenone derivatives, diazaphospholes (see the applicationWO 2010/054730) and triazines. However, there continues to be a demandfor alternative compounds for use as matrix components in mixed-matrixsystems. In particular, there is a demand for compounds which effect animprovement in the operating voltage and lifetime of the electronicdevices.

The applications WO 2007/031165 and WO 2006/033563 disclose triarylaminederivatives for use as functional materials in electronic devices. Inthe triarylamine compounds, the individual aryl groups are bridged toone another in a defined manner and are additionally substituted bycarbazole derivatives. However, the compounds disclosed therein containthree carbazole groups, which are arranged symmetrically around thecentral triarylamine group.

Bridged triarylamine derivatives are furthermore disclosed in theapplication WO 2010/083871.

However, there continues to be a demand for functional materials for usein OLEDs which preferably effect improvements in relation to theperformance data of the electronic devices, in particular in relation tothe lifetime and efficiency of the devices.

In particular, there is a demand for compounds which have high holemobility. This facilitates a low dependence of the operating voltage onthe thickness of the hole-transport layer, which represents a highlydesirable property. Furthermore, there is a demand for oxidation- andtemperature-stable compounds, since this improves the proccessability onuse in electronic devices.

The present invention provides compounds of the formula (1) and (2) inorder to achieve the technical object described above.

The invention thus relates to a compound of the formula (1) or (2)

where the following applies to the symbols and indices occurring:

-   -   W is on each occurrence equal to Z,        -   where a unit comprising two adjacent groups W may optionally            be replaced by a group of the formula (3)

-   -   -   where the group of the formula (3) is arranged in such a way            that the bond between the C atoms labelled with * is            condensed onto the six-membered ring of the carbazole            derivative;

    -   X is a divalent group selected from C(R)₂, Si(R)₂, NR, PR,        P(═O)R, BR, O, S, C═O, C═S, C═NR, S═O and S(═O)₂;

    -   Z is selected on each occurrence, identically or differently,        from CR and N, or is equal to C if a substituent is bonded to        the group Z;

    -   L is on each occurrence, identically or differently, a divalent        group selected from C(R)₂, Si(R)₂, NR, PR, P(═O)R, BR, O, S,        C═O, C═S, C═NR, C═C(R)₂, S═O, S(═O)₂ and CR═CR;

    -   R is, identically or differently on each occurrence, H, D, F,        Cl, Br, I, CHO, N(R¹)₂, C(═O)R¹, P(═O)(R¹)₂, S(═O)R¹, S(═O)₂R¹,        CR¹═C(R¹)₂, CN, NO₂, Si(R¹)₃, B(OR¹)₂, OSO₂R¹, OH, COOR¹,        CON(R¹)₂, a straight-chain alkyl, alkoxy or thioalkyl group        having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or        thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl        group having 2 to 40 C atoms, each of which may be substituted        by one or more radicals R¹, where one or more non-adjacent CH₂        groups may be replaced by —R¹C═CR¹—, —C≡C—, Si(R¹)₂, Ge(R¹)₂,        Sn(R¹)₂, C═O, C═S, C═Se, C═NR¹, P(═O)(R¹), SO, SO₂, NR¹, —O—,        —S—, —COO— or —CONR¹— and where one or more H atoms may be        replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic or        heteroaromatic ring system having 5 to 60 aromatic ring atoms,        which may in each case be substituted by one or more radicals        R¹, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic        ring atoms, which may be substituted by one or more radicals R¹,        or a combination of these systems, where two or more radicals R        may be linked to one another and may form a ring;

    -   R¹ is, identically or differently on each occurrence, H, D, F,        Cl, Br, I, CHO, N(R²)₂, C(═O)R², P(═O)(R²)₂, S(═O)R², S(═O)₂R²,        CR²═C(R²)₂, CN, NO₂, Si(R²)₃, B(OR²)₂, OSO₂R², OH, COOR²,        CON(R²)₂, a straight-chain alkyl, alkoxy or thioalkyl group        having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or        thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl        group having 2 to 40 C atoms, each of which may be substituted        by one or more radicals R², where one or more non-adjacent CH₂        groups may be replaced by —R²C═CR²—, —C≡C—, Si(R²)₂, Ge(R²)₂,        Sn(R²)₂, C═O, C═S, C═Se, C═NR², P(═O)(R²), SO, SO₂, NR², —O—,        —S—, —COO— or —CONR²— and where one or more H atoms may be        replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic or        heteroaromatic ring system having 5 to 60 aromatic ring atoms,        which may in each case be substituted by one or more radicals        R², or an aryloxy or heteroaryloxy group having 5 to 60 aromatic        ring atoms, which may be substituted by one or more radicals R²,        or a combination of these systems, where two or more radicals R¹        may be linked to one another and may form a ring;

    -   R² is, identically or differently on each occurrence, H, D, F or        an aliphatic, aromatic and/or heteroaromatic organic radical        having 1 to 20 C atoms, in which, in addition, one or more H        atoms may be replaced by D or F; two or more substituents R²        here may also be linked to one another and may form a ring;

    -   i is equal to 0, 1 or 2, where, for i=0, the two groups which        are bonded to the group with the index i are connected directly        to one another;

    -   j is equal to 0, 1 or 2, where, for j=0, the two groups which        are bonded to the group with the index j are connected directly        to one another;

    -   k is equal to 0 or 1, where, for k=0, the nitrogen atom and the        aromatic or heteroaromatic ring which are bonded to the group        with the index k are connected directly to one another;

    -   n is on each occurrence, identically or differently, 0 or 1,        where the sum of the values of the indices n can be equal to 1,        2 or 3;        and where furthermore a maximum of one substituent R may        represent a carbazole derivative,        and where the following structures are excluded:

An aryl group in the sense of this invention contains 6 to 60 C atoms; aheteroaryl group in the sense of this invention contains 1 to 60 C atomsand at least one heteroatom, with the proviso that the sum of C atomsand heteroatoms is at least 5. The heteroatoms are preferably selectedfrom N, O and/or S. An aryl group or heteroaryl group here is taken tomean either a simple aromatic ring, i.e. benzene, or a simpleheteroaromatic ring, for example pyridine, pyrimidine, thiophene, etc.,or a condensed (fused) aryl or heteroaryl group, for examplenaphthalene, anthracene, phenanthrene, quinoline, isoquinoline,carbazole, etc.

An aryl or heteroaryl group, which may in each case be substituted bythe above-mentioned radicals R or R¹ and which may be linked to thearomatic or heteroaromatic ring system via any desired positions, istaken to mean, in particular, groups derived from benzene, naphthalene,anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene,fluoranthene, benzanthracene, benzophenanthrene, tetracene, pentacene,benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene,benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole,isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine,phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline,benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole,imidazole, benzimidazole, naphthimidazole, phenanthrimidazole,pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole,benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole,1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine,pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine,naphthyridine, azacarbazole, benzocarboline, phenanthroline,1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole,1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole,1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine,1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine,1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine andbenzothiadiazole.

An aromatic ring system in the sense of this invention contains 6 to 60C atoms in the ring system. A heteroaromatic ring system in the sense ofthis invention contains 5 to 60 aromatic ring atoms, at least one ofwhich is a heteroatom. The heteroatoms are preferably selected from N, Oand/or S. An aromatic or heteroaromatic ring system in the sense of thisinvention is intended to be taken to mean a system which does notnecessarily contain only aryl or heteroaryl groups, but instead inwhich, in addition, a plurality of aryl or heteroaryl groups may beconnected by a non-aromatic unit (preferably less than 10% of the atomsother than H), such as, for example, an sp²-hybridised C, Si, N or Oatom, an sp²-hybridised C or N atom or an sp-hybridised C atom. Thus,for example, systems such as 9,9′-spirobifluorene, 9,9′-diarylfluorene,triarylamine, diaryl ether, stilbene, etc., are also intended to betaken to be aromatic ring systems in the sense of this invention, as aresystems in which two or more aryl groups are connected, for example, bya linear or cyclic alkyl, alkenyl or alkynyl group or by a silyl group.Furthermore, systems in which two or more aryl or heteroaryl groups arelinked to one another via one or more single bonds are also taken to bearomatic or heteroaromatic ring systems in the sense of this invention.

An aromatic or heteroaromatic ring system having 5-60 aromatic ringatoms, which may also in each case be substituted by radicals as definedabove and which may be linked to the aromatic or heteroaromatic groupvia any desired positions, is taken to mean, in particular, groupsderived from benzene, naphthalene, anthracene, benzanthracene,phenanthrene, benzophenanthrene, pyrene, chrysene, perylene,fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl,biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene,dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- ortrans-indenofluorene, truxene, isotruxene, spirotruxene,spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran,thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole,indole, isoindole, carbazole, pyridine, quinoline, isoquinoline,acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline,benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole,imidazole, benzimidazole, naphthimidazole, phenanthrimidazole,pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole,benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole,1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine,pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene,2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene,4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine,phenoxazine, phenothiazine, fluorubin, naphthyridine, azacarbazole,benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole,benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole,1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole,1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine,1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine,1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole orcombinations of these groups.

For the purposes of the present invention, a straight-chain alkyl grouphaving 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, inwhich, in addition, individual H atoms or CH₂ groups may be substitutedby the groups mentioned above under the definition of the radicals R andR¹, is preferably taken to mean the radicals methyl, ethyl, n-propyl,i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl,s-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl,n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl,trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl,propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl,heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl,butynyl, pentynyl, hexynyl or octynyl. An alkoxy or thioalkyl grouphaving 1 to 40 C atoms is preferably taken to mean methoxy,trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy,s-butoxy, t-butoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy,cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy,2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio,ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio,s-butylthio, t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio,cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio,cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio,pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio,propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio,cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio,cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio,hexynylthio, heptynylthio or octynylthio.

For the purposes of the present description, the formulation that two ormore radicals R (or R¹ or R²) may form a ring with one another isintended to be taken to mean, inter alia, that the two radicals arelinked to one another by a chemical bond. This is intended to beillustrated by the following scheme:

Furthermore, however, the above-mentioned formulation is also intendedto be taken to mean that, in the case where one of the two radicalsrepresents hydrogen, the second radical is bonded at the position atwhich the hydrogen atom was bonded, with formation of a ring. This isintended to be illustrated by the following scheme:

It should furthermore be emphasized for clarity that, for the purposesof the present description, an aromatic or heteroaromatic ring may alsobe represented by a central circle in the ring as an alternative to theclassical Lewis notation.

Furthermore, the numbering used for the purposes of the presentdescription in the carbazole skeleton will be presented at this point:

For the purposes of the present description, the formulation that a unitcomprising two adjacent groups W (unit W—W) has been replaced by a groupof the formula (3) is taken to mean that a group of the formula (3)

is present instead of the two adjacent groups W.

The C atoms labelled with * here adopt the positions in the six-memberedring which were previously occupied by the unit W—W. Consequently, thegroup of the formula (3) is condensed onto the six-membered ring whichhad previously contained the unit W—W.

It is preferred for a maximum of one unit W—W per six-membered ring inthe compound according to the invention to have been replaced by a groupof the formula (3). All other groups W in this six-membered ring are inthis case equal to Z.

An example of a compound according to the invention in which a unit W—Whas been replaced by a group of the formula (3) is the followingcompound of the formula (8).

In a further preferred embodiment of the invention, only one unit W—W inthe compounds of the formula (1) or (2) according to the invention hasbeen replaced by a group of the formula (3).

In a further preferred embodiment of the invention, all groups W informula (1) or (2) are equal to Z, and no unit W—W has been replaced bya group of the formula (3).

In a further preferred embodiment of the invention, the compoundsaccording to the invention are represented by the formulae (4) to (14).

where the symbols and indices occurring are as defined above.

It is preferred in accordance with the invention for the bond from thecarbazole group in the compounds of the formula (2) to emanate from the2- or 3-position.

Particularly preferred embodiments of the compounds of the formula (1)or (2) conform to the following formulae (15) to (74):

where the symbols and indices occurring are as defined above.

In a preferred embodiment of the invention, Z is equal to CR or, if asubstituent is bonded to group Z, is equal to C. This preference appliesto all embodiments of the compounds according to the invention.

It is furthermore preferred for L to be selected on each occurrence,identically or differently, from C(R)₂, NR, O, S, C═O, C═NR, S═O, S(═O)₂and CR═CR. L is particularly preferably selected from C(R)₂, NR, O, S,S═O and S(═O)₂. L is very particularly preferably selected from CR₂ andNR.

In a further preferred embodiment of the invention, in the case wherethe sum of the values of the indices n is equal to 2 or 3, at least onegroup L is selected from NR, O, S, C═O, C═NR, S═O, S(═O)₂ and CR═CR,particularly preferably from NR, O, S, S═O and S(═O)₂.

In a preferred embodiment of the invention, X is selected from C(R)₂,NR, O, S, C═O, C═NR, S═O and S(═O)₂. X is particularly preferablyselected from C(R)₂, NR, O, S, S═O and S(═O)₂. X is very particularlypreferably selected from CR₂ and NR.

In a preferred embodiment of the invention, k is equal to 1.

In a further preferred embodiment of the invention, i is equal to 0 or1.

In a further preferred embodiment of the invention, j is equal to 0 or1.

In a further preferred embodiment of the invention, the sum of thevalues of the indices n is equal to 1 or 2.

In a preferred embodiment of the invention, a radical R which is part ofa group Z in the embodiment CR represents carbazole or a carbazolederivative.

In a preferred embodiment of the invention, the compounds of the formula(1) and (2) only contain a single carbazole group. In this connection, acondensed heteroaromatic ring system, such as, for example,indenocarbazole or indolocarbazole, will by definition only count as asingle carbazole group.

For the compounds according to the invention, it is preferred for amaximum of one substituent R to represent carbazole or a carbazolederivative. In a preferred embodiment of the invention, no radical R inthe compounds according to the invention represents a carbazolederivative. A carbazole derivative here is taken to mean a carbazolewhich is substituted as desired.

The radical R is preferably selected on each occurrence, identically ordifferently, from H, D, F, CN, Si(R¹)₃, N(R¹)₂ or a straight-chain alkylor alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl oralkoxy group having 3 to 20 C atoms, each of which may be substituted byone or more radicals R¹, where one or more adjacent or non-adjacent CH₂groups may be replaced by —C≡C—, —R¹C═CR¹—, Si(R¹)₂, C═O, C═NR¹, —NR¹—,—O—, —S—, —COO— or —CONR¹—, or an aryl or heteroaryl group having 5 to30 aromatic ring atoms, which may in each case be substituted by one ormore radicals R¹, where two or more radicals R may be linked to oneanother and may form a ring.

The radical R¹ is preferably selected on each occurrence, identically ordifferently, from H, D, F, CN, Si(R²)₃, N(R²)₂ or a straight-chain alkylor alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl oralkoxy group having 3 to 20 C atoms, each of which may be substituted byone or more radicals R², where one or more adjacent or non-adjacent CH₂groups may be replaced by —C≡C—, —R²C═CR²—, Si(R²)₂, C═O, C═NR², —NR²—,—O—, —S—, —COO— or —CONR²—, or an aryl or heteroaryl group having 5 to30 aromatic ring atoms, which may in each case be substituted by one ormore radicals R², where two or more radicals R¹ may be linked to oneanother and may form a ring.

In a further preferred embodiment of the invention, the radicals R arenot linked to one another and do not form a ring.

In a further preferred embodiment of the invention, the radicals R¹ arenot linked to one another and do not form a ring.

The general and preferred embodiments mentioned above can in accordancewith the invention be combined with one another as desired.

For the purposes of the present invention, it is preferred for therespective preferred embodiments of the groups and indices L, X, R, R¹,n, k, i and j to occur in combination with the preferred embodiments inaccordance with the formulae (4) to (14) and the particularly preferredembodiments in accordance with the formulae (15) to (74).

Examples of compounds according to the invention are given in thefollowing table:

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

55

56

57

58

59

60

61

62

63

64

65

66

67

68

69

70

71

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

87

88

89

90

91

92

93

94

95

96

97

98

99

100

101

102

103

104

105

106

107

108

109

110

111

112

113

114

115

The compounds according to the invention can be prepared by syntheticsteps which are known to the person skilled in the art, such as, forexample, bromination, Suzuki coupling, Hartwig-Buchwald coupling, etc.

Examples of synthetic routes which lead to the compounds according tothe invention will be shown below. The radical R here is as definedabove.

In Scheme 1, the carbazole derivative shown (CAS 1028647-93-9) isfirstly reacted with a carboxylate-substituted arylamine in a Buchwaldcoupling. A cyclization reaction is subsequently carried out after theaddition reaction of two groups R by means of an organolithium reagent.The bridge is thus introduced via a divalent group —C(R)₂—. Asubstituent can subsequently be introduced on the free amino function ofthe resultant piperidine derivative via a Buchwald coupling.

The synthesis of N-aryl-substituted carbazole derivatives, which isshown in Scheme 2, proceeds substantially analogously. The startingcompound is the N-arylcarbazole derivative shown below (CAS212385-73-4).

The divalent bridging group C(R)₂ may also be localized at anotherposition in the compounds according to the invention. An example thereofis provided by Scheme 3a. To this end, the synthesis starts directlyfrom a 9,10-dihydroacridine derivative, which can be reacted with a3-bromine-substituted carbazole in a Buchwald coupling.

Alternatively, the reaction can also be carried out with anN-aryl-substituted carbazole, as shown by Scheme 3b.

Arylamine derivatives which are multiply bridged by divalent groups canalso be reacted with the carbazole derivatives shown. This givescompounds according to the invention in which two or three groups L arepresent.

The synthesis of two precursors of this type which contain two groups Lis shown in Scheme 4a and b.

The divalent groups —C(R)₂— are in this case obtained again by theaddition of organolithium compounds onto the aromatic carboxylate groupwith subsequent acid-catalyzed cyclization.

It is furthermore possible to prepare compounds which are analogous tothe compounds shown in Scheme 4, but which contain one or more bridginggroups such as, for example, O, S or SO₂ instead of one or more bridginggroups —CR₂—. As shown in the synthesis examples, the unbrominatedstarting compounds are in many cases commercially available.

The synthesis of triarylamine compounds which contain three bridginggroups L (for example —CR₂— and —O—) is disclosed in the application WO2007/031165.

Scheme 5a shows the synthesis of compounds according to the inventionstarting from the doubly bridged triarylamine precursor shown in Scheme4a. Schemes 5b and 5c show analogously the synthesis of compoundsaccording to the invention starting from the doubly bridged triarylamineprecursor shown in Scheme 4 or starting from triarylamine compoundswhich contain three bridging groups L. Suzuki coupling reactionsstarting from boronic acid-substituted carbazole derivatives areemployed here. Processes for the synthesis of boronic acid derivativesfrom the corresponding bromine-substituted derivatives are known to theperson skilled in the art.

Instead of the starting compounds shown above, it is also possibleanalogously to employ compounds which contain one or more bridginggroups such as, for example, O, S or SO₂ instead of the groups CR₂ shownabove.

It is also possible to use the corresponding indeno- or indolocarbazolederivatives instead of the carbazole derivatives employed in the aboveschemes.

Examples of corresponding indeno- and indolocarbazole derivatives areshown in Scheme 6 below.

The synthesis of indenocarbazole derivatives, which can be employed asintermediates in the synthesis of the compounds according to theinvention, is described, inter alia, in the application WO 2010/083873and in the as yet unpublished applications DE 102009023155.2 and DE102009031021.5. Furthermore, the synthesis of the indeno- orindolo-carbazole derivatives may be known from the literature, such as,for example, in the case of the indolocarbazole depicted on the left inScheme 6 (CAS 222044-88-4 for the unbrominated derivative).

The indeno- and indolocarbazole-based compounds according to theinvention can in principle be prepared by the same synthetic routes asthe corresponding carbazole-based compounds according to the inventionby replacing the carbazole derivatives serving as intermediates bycorresponding indeno- or indolocarbazole derivatives (cf. Schemes 1-5).

The present invention thus relates to a process for the preparation ofcompounds of the formula (1) or (2), comprising at least one couplingreaction for the linking of the moiety containing the carbazole group tothe moiety containing the arylamino group. In a preferred embodiment ofthis process, a Suzuki, Hartwig-Buchwald, Stille or Yamamoto coupling isemployed for the linking of the two moieties. Particularly preferredembodiments of processes for the preparation of the compounds accordingto the invention are the processes depicted in the schemes above.

The compounds according to the invention described above, in particularcompounds which are substituted by reactive leaving groups, such asbromine, iodine, chlorine, boronic acid or boronic acid ester, can beused as monomers for the preparation of corresponding oligomers,dendrimers or polymers. The oligomerisation or polymerisation here ispreferably carried out via the halogen functionality or the boronic acidfunctionality.

The invention therefore furthermore relates to oligomers, polymers ordendrimers comprising one or more compounds of the formula (1) or (2),where the bond(s) to the polymer, oligomer or dendrimer may be localizedat any desired positions substituted by R in formula (1) or (2).Depending on the linking of the compound of the formula (1) or (2), thecompound is part of a side chain of the oligomer or polymer or part ofthe main chain. An oligomer in the sense of this invention is taken tomean a compound which is built up from at least three monomer units. Apolymer in the sense of the invention is taken to mean a compound whichis built up from at least ten monomer units. The polymers, oligomers ordendrimers according to the invention may be conjugated, partiallyconjugated or non-conjugated. The oligomers or polymers according to theinvention may be linear, branched or dendritic. In the structures linkedin a linear manner, the units of the formula (1) or (2) may be linkeddirectly to one another or linked to one another via a divalent group,for example via a substituted or unsubstituted alkylene group, via aheteroatom or via a divalent aromatic or heteroaromatic group. Inbranched and dendritic structures, three or more units of the formula(1) or (2) may, for example, be linked via a trivalent or poly-valentgroup, for example via a trivalent or polyvalent aromatic orhetero-aromatic group, to give a branched or dendritic oligomer orpolymer. For the recurring units of the formula (1) or (2) in oligomers,dendrimers and polymers, the same preferences apply as described abovefor compounds of the formula (1) or (2).

For the preparation of the oligomers or polymers, the monomers accordingto the invention are homopolymerised or copolymerised with furthermonomers. Suitable and preferred comonomers are selected from fluorenes(for example in accordance with EP 842208 or WO 00/22026),spirobifluorenes (for example in accordance with EP 707020, EP 894107 orWO 06/061181), para-phenylenes (for example in accordance with WO92/18552), carbazoles (for example in accordance with WO 04/070772 or WO04/113468), thiophenes (for example in accordance with EP 1028136),dihydrophenanthrenes (for example in accordance with WO 05/014689 or WO07/006383), cis- and trans-indenofluorenes (for example in accordancewith WO 04/041901 or WO 04/113412), ketones (for example in accordancewith WO 05/040302), phenanthrenes (for example in accordance with WO05/104264 or WO 07/017066) or also a plurality of these units. Thepolymers, oligomers and dendrimers usually also contain further units,for example emitting (fluorescent or phosphorescent) units, such as, forexample, vinyltriarylamines (for example in accordance with WO2007/068325) or phosphorescent metal complexes (for example inaccordance with WO 2006/003000), and/or charge-transport units, inparticular those based on triarylamines.

The polymers, oligomers and dendrimers according to the invention haveadvantageous properties, in particular long lifetimes, high efficienciesand good colour coordinates.

The polymers and oligomers according to the invention are generallyprepared by polymerisation of one or more types of monomer, at least onemonomer of which results in recurring units of the formula (1) or (2) inthe polymer. Suitable polymerisation reactions are known to the personskilled in the art and are described in the literature. Particularlysuitable and preferred polymerisation reactions which result in C—C orC—N links are the following:

(A) SUZUKI polymerisation;

(B) YAMAMOTO polymerisation;

(C) STILLE polymerisation; and

(D) HARTWIG-BUCHWALD polymerisation.

The way in which the polymerisation can be carried out by these methodsand the way in which the polymers can then be separated off from thereaction medium and purified is known to the person skilled in the artand is described in detail in the literature, for example in WO2003/048225, WO 2004/037887 and WO 2004/037887.

The present invention thus also relates to a process for the preparationof the polymers, oligomers and dendrimers according to the invention,which is characterised in that they are prepared by SUZUKIpolymerisation, YAMAMOTO polymerisation, STILLE polymerisation orHARTWIG-BUCHWALD polymerisation. The dendrimers according to theinvention can be prepared by processes known to the person skilled inthe art or analogously thereto. Suitable processes are described in theliterature, such as, for example, in Frechet, Jean M. J.; Hawker, CraigJ., “Hyper-branched polyphenylene and hyperbranched polyesters: newsoluble, three-dimensional, reactive polymers”, Reactive & FunctionalPolymers (1995), 26(1-3), 127-36; Janssen, H. M.; Meijer, E. W., “Thesynthesis and characterization of dendritic molecules”, MaterialsScience and Technology (1999), 20 (Synthesis of Polymers), 403-458;Tomalia, Donald A., “Dendrimer molecules”, Scientific American (1995),272(5), 62-6; WO 02/067343 A1 and WO 2005/026144 A1.

The invention also relates to formulations comprising at least onecompound of the formula (1) or (2) or at least one polymer, oligomer ordendrimer containing at least one unit of the formula (1) or (2) and atleast one solvent, preferably an organic solvent.

The formulations according to the invention are used, for example, inthe production of organic electroluminescent devices, which is describedin greater detail in a following section.

The compounds of the formula (1) or (2) according to the invention aresuitable for use in electronic devices, in particular in organicelectroluminescent devices (OLEDs). Depending on the substitution, thecompounds are employed in various functions and in various layers of theorganic electroluminescent device.

The invention therefore furthermore relates to the use of the compoundsof the formula (1) or (2) according to the invention in electronicdevices. The electronic devices here are preferably selected from thegroup consisting of organic integrated circuits (O-ICs), organicfield-effect transistors (O-FETs), organic thin-film transistors(O-TFTs), organic light-emitting transistors (O-LETs), organic solarcells (O-SCs), organic optical detectors, organic photoreceptors,organic field-quench devices (O-FQDs), light-emitting electrochemicalcells (LECs), organic laser diodes (O-lasers) and particularlypreferably organic electroluminescent devices (OLEDs).

Particular preference is given to organic electroluminescent devicescomprising an anode, a cathode and at least one emitting layer,characterised in that at least one organic layer, which may be anemitting layer, a hole-transport layer or another layer, comprises atleast one compound of the formula (1) or (2).

Apart from the cathode, anode and emitting layer, the organicelectroluminescent device may also comprise further layers. These areselected, for example, from in each case one or more hole-injectionlayers, hole-transport layers, hole-blocking layers, electron-transportlayers, electron-injection layers, electron-blocking layers,exciton-blocking layers, interlayers, charge-generation layers (IDMC2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K.Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL DeviceHaving Charge Generation Layer) and/or organic or inorganic p/njunctions. However, it should be pointed out that each of these layersdoes not necessarily have to be present and the choice of layers isalways dependent on the compounds used and in particular also on whetherthe electroluminescent device is fluorescent or phosphorescent.

The organic electroluminescent device may also comprise a plurality ofemitting layers. These emission layers in this case particularlypreferably have in total a plurality of emission maxima between 380 nmand 750 nm, resulting overall in white emission, i.e. various emittingcompounds which are able to fluoresce or phosphoresce and which emitblue and yellow, orange or red light are used in the emitting layers.Particular preference is given to three-layer systems, i.e. systemshaving three emitting layers, where at least one of these layerscomprises at least one compound of the formula (1) or (2) and where thethree layers exhibit blue, green and orange or red emission (for thebasic structure see, for example, WO 2005/011013). Alternatively and/oradditionally, the compounds according to the invention may also bepresent in the hole-transport layer. Emitters which have broad-bandemission bands and thus exhibit white emission are likewise suitable forwhite emission.

It is preferred in accordance with the invention for the compound of theformula (1) or (2) to be employed in an electronic device comprising oneor more phosphorescent dopants. The compound here can be used in variouslayers, preferably in a hole-transport layer, a hole-injection layer orin the emitting layer. However, the compound of the formula (1) or (2)can also be employed in accordance with the invention in an electronicdevice comprising one or more fluorescent dopants.

Suitable phosphorescent dopants (=triplet emitters) are, in particular,compounds which emit light, preferably in the visible region, onsuitable excitation and in addition contain at least one atom having anatomic number greater than 20, preferably greater than 38 and less than84, particularly preferably greater than 56 and less than 80. Thephosphorescent emitters used are preferably compounds which containcopper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium,iridium, palladium, platinum, silver, gold or europium, in particularcompounds which contain iridium, platinum or Cu.

For the purposes of the present invention, all luminescent iridium,platinum or copper complexes are regarded as phosphorescent compounds.

Examples of the emitters described above are revealed by theapplications WO 00/70655, WO 01/41512, WO 02/02714, WO 02/15645, EP1191613, EP 1191612, EP 1191614, WO 05/033244, WO 05/019373 and US2005/0258742. In general, all phosphorescent complexes as used inaccordance with the prior art for phosphorescent OLEDs and as are knownto the person skilled in the art in the area of organicelectroluminescent devices are suitable. The person skilled in the artwill also be able to employ further phosphorescent complexes withoutinventive step in combination with the compounds of the formula (1) or(2) according to the invention in organic electroluminescent devices.

Examples of suitable phosphorescent emitter compounds are furthermorerevealed by the following table:

In a preferred embodiment of the invention, the compounds of the formula(1) or (2) are employed as hole-transport material. The compounds arethen preferably employed in a hole-transport layer and/or in ahole-injection layer. For the purposes of this invention, ahole-injection layer is a layer which is directly adjacent to the anode.For the purposes of this invention, a hole-transport layer is a layerwhich is located between the hole-injection layer and the emissionlayer. The hole-transport layer may be directly adjacent to the emissionlayer. If the compounds of the formula (1) or (2) are used ashole-transport material or as hole-injection material, it may bepreferred for them to be doped with electron-acceptor compounds, forexample with F₄-TCNQ or with compounds as described in EP 1476881 or EP1596445. In a further preferred embodiment of the invention, a compoundof the formula (1) or (2) is used as hole-transport material incombination with a hexaazatriphenylene derivative as described in US2007/0092755. The hexaazatriphenylene derivative is particularlypreferably employed in its own layer here.

If the compound of the formula (1) or (2) is employed as hole-transportmaterial in a hole-transport layer, the compound can be employed as purematerial, i.e. in a proportion of 100% in the hole-transport layer, orit can be employed in combination with one or more further compounds inthe hole-transport layer.

In a further embodiment of the present invention, the compounds of theformula (1) or (2) are employed as matrix material in combination withone or more dopants, preferably phosphorescent dopants.

A dopant is taken to mean the component whose proportion in the mixtureis the smaller in a system comprising a matrix material and a dopant.Correspondingly, a matrix material is taken to mean the component whoseproportion in the mixture is the greater in a system comprising a matrixmaterial and a dopant.

The proportion of the matrix material in the emitting layer is in thiscase between 50.0 and 99.9% by vol., preferably between 80.0 and 99.5%by vol. and particularly preferably between 92.0 and 99.5% by vol. forfluorescent emitting layers and between 85.0 and 97.0% by vol. forphosphorescent emitting layers.

Correspondingly, the proportion of the dopant is between 0.1 and 50.0%by vol., preferably between 0.5 and 20.0% by vol. and particularlypreferably between 0.5 and 8.0% by vol. for fluorescent emitting layersand between 3.0 and 15.0% by vol. for phosphorescent emitting layers.

An emitting layer of an organic electroluminescent device may alsocomprise systems comprising a plurality of matrix materials(mixed-matrix systems) and/or a plurality of dopants. In this case too,the dopants are generally the materials whose proportion in the systemis the smaller and the matrix materials are the materials whoseproportion in the system is the greater. In individual cases, however,the proportion of an individual matrix material in the system may besmaller than the proportion of an individual dopant.

In a preferred embodiment of the invention, the compounds of the formula(1) or (2) are used as a component of mixed matrix systems. Themixed-matrix systems preferably comprise two or three different matrixmaterials, particularly preferably two different matrix materials. Thetwo different matrix materials here may be present in a ratio of 1:10 to1:1, preferably in a ratio of 1:4 to 1:1. The mixed-matrix systems maycomprise one or more dopants. The dopant compound or the dopantcompounds together have, in accordance with the invention, a proportionof 0.1 to 50.0% by vol. in the mixture as a whole and preferably aproportion of 0.5 to 20.0% by vol. in the mixture as a whole.Correspondingly, the matrix components together have a proportion of50.0 to 99.9% by vol. in the mixture as a whole and preferably aproportion of 80.0 to 99.5% by vol. in the mixture as a whole.

Mixed-matrix systems are preferably employed in phosphorescent organicelectroluminescent devices.

Particularly suitable matrix materials, which can be employed incombination with the compounds according to the invention as matrixcomponents of a mixed-matrix system, are aromatic ketones, aromaticphosphine oxides or aromatic sulfoxides or sulfones, for example inaccordance with WO 04/013080, WO 04/093207, WO 06/005627 or theunpublished application DE 102008033943.1, triarylamines, carbazolederivatives, for example CBP (N,N-biscarbazolylbiphenyl) or thecarbazole derivatives disclosed in WO 05/039246, US 2005/0069729, JP2004/288381, EP 1205527 or WO 08/086851, indolocarbazole derivatives,for example in accordance with WO 07/063754 or WO 08/056746,azacarbazole derivatives, for example in accordance with EP 1617710, EP1617711, EP 1731584, JP 2005/347160, bipolar matrix materials, forexample in accordance with WO 07/137725, silanes, for example inaccordance with WO 05/111172, azaboroles or boronic esters, for examplein accordance with WO 06/117052, triazine derivatives, for example inaccordance with the application WO 2010/015306, WO 2007/063754 or WO2008/056746, zinc complexes, for example in accordance with EP 652273 orWO 09/062578, diazasilole or tetraazasilole derivatives, for example inaccordance with the application WO 2010/054729, diazaphospholederivatives, for example in accordance with the application WO2010/054730, or indenocarbazole derivatives, for example in accordancewith the unpublished application DE 102009023155.2.

Preferred phosphorescent dopants for use in mixed-matrix systemscomprising the compounds according to the invention are thephosphorescent dopants mentioned in the above table.

In a further embodiment of the invention, the compounds of the formula(1) or (2) are employed as emitting materials in an emitting layer. Thecompounds are suitable, in particular, as emitting compounds if theycontain a plurality of diarylamino groups. In this case, the compoundsaccording to the invention are particularly preferably used as green orblue emitters.

Preferred matrix materials for use in combination with the compoundsaccording to the invention as fluorescent emitters are mentioned in oneof the following sections.

The materials preferably employed for the respective functions in theelectronic devices according to the invention are mentioned below.

Preferred fluorescent emitter materials are selected from the class ofthe monostyrylamines, the distyrylamines, the tristyrylamines, thetetrastyrylamines, the styrylphosphines, the styryl ethers and thearylamines. A monostyrylamine is taken to mean a compound which containsone substituted or unsubstituted styryl group and at least one,preferably aromatic, amine. A distyrylamine is taken to mean a compoundwhich contains two substituted or unsubstituted styryl groups and atleast one, preferably aromatic, amine. A tristyrylamine is taken to meana compound which contains three substituted or unsubstituted styrylgroups and at least one, preferably aromatic, amine. A tetrastyrylamineis taken to mean a compound which contains four substituted orunsubstituted styryl groups and at least one, preferably aromatic,amine. The styryl groups are particularly preferably stilbenes, whichmay also be further substituted. Corresponding phosphines and ethers aredefined analogously to the amines. An arylamine or aromatic amine in thesense of this invention is taken to mean a compound which contains threesubstituted or unsubstituted aromatic or heteroaromatic ring systemsbonded directly to the nitrogen. At least one of these aromatic orheteroaromatic ring systems is preferably a condensed ring system,particularly preferably having at least 14 aromatic ring atoms.

Preferred examples thereof are aromatic anthracenamines, aromaticanthracenediamines, aromatic pyrenamines, aromatic pyrenediamines,aromatic chrysenamines or aromatic chrysenediamines. An aromaticanthracenamine is taken to mean a compound in which one diarylaminogroup is bonded directly to an anthracene group, preferably in the9-position. An aromatic anthracenediamine is taken to mean a compound inwhich two diarylamino groups are bonded directly to an anthracene group,preferably in the 9,10-position. Aromatic pyrenamines, pyrenediamines,chrysenamines and chrysenediamines are defined analogously thereto,where the diarylamino groups are preferably bonded to the pyrene in the1-position or in the 1,6-position. Further preferred emitter materialsare selected from indenofluorenamines or indenofluorenediamines, forexample in accordance with WO 06/122630, benzoindenofluorenamines orbenzoindenofluorenediamines, for example in accordance with WO08/006449, and dibenzoindenofluorenamines ordibenzoindenofluorenediamines, for example in accordance with WO07/140847. Examples of emitter materials from the class of thestyrylamines are substituted or unsubstituted tristilbenamines or theemitter materials described in WO 06/000388, WO 06/058737, WO 06/000389,WO 07/065549 and WO 07/115610. Preference is furthermore given to thecondensed hydrocarbons disclosed in the application WO 2010/012328.

Preferred emitter materials are furthermore the compounds of the formula(1) or (2) according to the invention.

Suitable emitter materials are furthermore the structures depicted inthe following table, and the derivatives of these structures disclosedin JP 06/001973, WO 04/047499, WO 06/098080, WO 07/065678, US2005/0260442 and WO 04/092111.

Suitable matrix materials, preferably for fluorescent dopants, arematerials from various classes of substance. Preferred matrix materialsare selected from the classes of the oligoarylenes (for example2,2′,7,7-tetraphenyl-spirobifluorene in accordance with EP 676461 ordinaphthylanthracene), in particular the oligoarylenes containingcondensed aromatic groups, the oligoarylenevinylenes (for example DPVBior spiro-DPVBi in accordance with EP 676461), the polypodal metalcomplexes (for example in accordance with WO 04/081017), thehole-conducting compounds (for example in accordance with WO 04/058911),the electron-conducting compounds, in particular ketones, phosphineoxides, sulfoxides, etc. (for example in accordance with WO 05/084081and WO 05/084082), the atropisomers (for example in accordance with WO06/048268), the boronic acid derivatives (for example in accordance withWO 06/117052) or the benzanthracenes (for example in accordance with WO08/145239). Suitable matrix materials are furthermore preferably thecompounds according to the invention. Apart from the compounds accordingto the invention, particularly preferred matrix materials are selectedfrom the classes of the oligoarylenes, comprising naphthalene,anthracene, benzanthracene and/or pyrene or atropisomers of thesecompounds, the oligoarylenevinylenes, the ketones, the phosphine oxidesand the sulfoxides. Apart from the compounds according to the invention,very particularly preferred matrix materials are selected from theclasses of the oligoarylenes, comprising anthracene, benzanthracene,benzophenanthrene and/or pyrene or atropisomers of these compounds. Anoligoarylene in the sense of this invention is intended to be taken tomean a compound in which at least three aryl or arylene groups arebonded to one another.

Suitable matrix materials, preferably for fluorescent dopants, are, forexample, the materials depicted in the following table, and derivativesof these materials, as disclosed in WO 04/018587, WO 08/006449, U.S.Pat. No. 5,935,721, US 2005/0181232, JP 2000/273056, EP 681019, US2004/0247937 and US 2005/0211958.

Besides the compounds according to the invention, suitablecharge-transport materials, as can be used in the hole-injection orhole-transport layer or in the electron-transport layer of the organicelectroluminescent device according to the invention, are, for example,the compounds disclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4),953-1010, or other materials as are employed in these layers inaccordance with the prior art.

The cathode of the organic electroluminescent device preferablycomprises metals having a low work function, metal alloys ormultilayered structures comprising various metals, such as, for example,alkaline-earth metals, alkali metals, main-group metals or lanthanoids(for example Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable arealloys comprising an alkali metal or alkaline-earth metal and silver,for example an alloy comprising magnesium and silver. In the case ofmultilayered structures, further metals which have a relatively highwork function, such as, for example, Ag or Al, can also be used inaddition to the said metals, in which case combinations of the metals,such as, for example, Ca/Ag or Ba/Ag, are generally used. It may also bepreferred to introduce a thin interlayer of a material having a highdielectric constant between a metallic cathode and the organicsemiconductor. Suitable for this purpose are, for example, alkali metalfluorides or alkaline-earth metal fluorides, but also the correspondingoxides or carbonates (for example LiF, Li₂O, BaF₂, MgO, NaF, CsF,Cs₂CO₃, etc.). Furthermore, lithium quinolinate (LiQ) can be used forthis purpose. The layer thickness of this layer is preferably between0.5 and 5 nm.

The anode preferably comprises materials having a high work function.The anode preferably has a work function of greater than 4.5 eV vs.vacuum. Suitable for this purpose are on the one hand metals having ahigh redox potential, such as, for example, Ag, Pt or Au. On the otherhand, metal/metal oxide electrodes (for example Al/Ni/NiO_(x),Al/PtO_(x)) may also be preferred. For some applications, at least oneof the electrodes must be transparent in order to facilitate eitherirradiation of the organic material (organic solar cells) or thecoupling-out of light (OLEDs, O-lasers). A preferred structure uses atransparent anode. Preferred anode materials here are conductive mixedmetal oxides. Particular preference is given to indium tin oxide (ITO)or indium zinc oxide (IZO). Preference is furthermore given toconductive, doped organic materials, in particular conductive, dopedpolymers.

The device is appropriately (depending on the application) structured,provided with contacts and finally sealed, since the lifetime of thedevices according to the invention is shortened in the presence of waterand/or air.

In a preferred embodiment, the organic electroluminescent deviceaccording to the invention is characterised in that one or more layersare applied by means of a sublimation process, in which the materialsare applied by vapour deposition in vacuum sublimation units at aninitial pressure of less than 10⁻⁵ mbar, preferably less than 10⁻⁶ mbar.However, it is also possible here for the initial pressure to be evenlower, for example less than 10⁻⁷ mbar.

Preference is likewise given to an organic electroluminescent device,characterised in that one or more layers are applied by means of theOVPD (organic vapour phase deposition) process or with the aid ofcarrier-gas sublimation, in which the materials are applied at apressure of between 10⁻⁵ mbar and 1 bar. A special case of this processis the OVJP (organic vapour jet printing) process, in which thematerials are applied directly through a nozzle and are thus structured(for example M. S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

Preference is furthermore given to an organic electroluminescent device,characterised in that one or more layers are produced from solution,such as, for example, by spin coating, or by means of any desiredprinting process, such as, for example, screen printing, flexographicprinting, nozzle printing or offset printing, but particularlypreferably LITI (light induced thermal imaging, thermal transferprinting) or ink-jet printing. Soluble compounds of the formula (1) or(2) are necessary for this purpose. High solubility can be achievedthrough suitable substitution of the compounds.

For the production of an organic electroluminescent device according tothe invention, it is furthermore preferred to apply one or more layersfrom solution and one or more layers by a sublimation process.

In accordance with the invention, the electronic devices comprising oneor more compounds of the formula (1) or (2) can be employed in displays,as light sources in lighting applications and as light sources inmedical and/or cosmetic applications (for example light therapy).

The compounds according to the invention are distinguished by good holemobility. On use in a hole-transport layer, the compounds thereforeexhibit a low dependence of the operating voltage on the thickness ofthe hole-transport layer.

Furthermore, the compounds according to the invention are distinguishedby high oxidation and temperature stability, which has a positive effecton the proccessability and lifetime of the electronic devices comprisingthe materials.

The compounds are furthermore very highly suitable for use as matrixmaterials in mixed-matrix systems, where they preferably result in areduction in the operating voltage and an increase in the lifetime ofthe electronic devices.

In summary, the compounds according to the invention effect one or moreof the above-mentioned advantages on use in electronic devices, namelyan increase in the efficiency of the device, an increase in the lifetimeand/or a reduction in the operating voltage.

The invention is explained in greater detail by the following workingexamples, without wishing it to be restricted thereby.

USE EXAMPLES A) SYNTHESIS EXAMPLES

The following syntheses were carried out, unless indicated otherwise,under a protective-gas atmosphere. The starting materials were purchasedfrom ALDRICH or ABCR.

Example 1 Synthesis of10-biphenyl-4-yl-9,9-dimethyl-2-(9-phenyl-9H-carbazol-3-yl)-9,10-dihydroacridine(HTM2)

a) Methyl 2-[4-(9-phenyl-9H-carbazol-3-yl)phenylamino]benzoate

Caesium carbonate (25.4 g, 78 mmol), palladium acetate (0.9 g, 4 mmol)and xantphos (1.5 g, 8 mmol) are added to a solution of3-(4-bromophenyl)-9-phenyl-9H-carbazole (CAS 1028647-93-9, 31.0 g, 78mmol) and methyl anthranilate (10.1 ml, 78 mmol) in degassed toluene(300 ml), and the mixture is heated under reflux for 8 h. Theprecipitated salts are filtered off, and the mother liquor is evaporatedin vacuo. The residue is extracted with chloroform in a Soxhletextractor and subsequently recrystallized from toluene.

Yield: 26.0 g (55 mmol), 71% of theory, colourless solid.

b) 9,9-Dimethyl-2-(9-phenyl-9H-carbazol-3-yl)-9,10-dihydroacridine

Methyl 2-[4-(9-phenyl-9H-carbazol-3-yl)phenylamino]benzoate (26.0 g, 55mmol) is added in portions to a suspension of anhydrous cerium(III)chloride (15.0 g, 61 mmol) in dried tetrahydrofuran (400 ml). A 3 Msolution of methylmagnesium chloride in tetrahydrofuran (56.2 ml, 169mmol) is subsequently added dropwise at 0° C., and the mixture isstirred at room temperature for 20 h. The reaction mixture isneutralized using 25% acetic acid (about 55 ml) with ice-cooling anddiluted with dist. water and ethyl acetate. The aqueous phase isextracted with ethyl acetate, dried over sodium sulfate and evaporatedin vacuo.

The residue is dissolved in dichloromethane (100 ml) and added dropwiseover the course of 20 min to a solution of polyphosphoric acid (43.4 g,376 mmol) and methanesulfonic acid (24.9 ml, 379 mmol) indichloromethane (100 ml). The reaction mixture is stirred at roomtemperature for 1 h and subsequently evaporated in vacuo. The residue istaken up in ethyl acetate, washed with dist. water, dried over sodiumsulfate and evaporated in vacuo. The crude product is dissolved in ethylacetate/dichloromethane (15/1), filtered through basic aluminium oxideand purified by recrystallization from ethyl acetate.

Yield: 18.7 g (42 mmol), 75% of theory, colourless solid.

c)10-Biphenyl-4-yl-9,9-dimethyl-2-(9-phenyl-9H-carbazol-3-yl)-9,10-dihydroacridine

Caesium carbonate (26.0 g, 80 mmol), palladium acetate (0.4 g, 2 mmol)and xantphos (0.8 g, 4 mmol) are added to a solution of9,9-dimethyl-2-(9-phenyl-9H-carbazol-3-yl)-9,10-dihydroacridine (18.0 g,40 mmol) and 4-bromobiphenyl (9.3 g, 40 mmol) in degassed toluene (250ml), and the mixture is heated under reflux for 8 h. The precipitatedsalts are filtered off, and the mother liquor is evaporated in vacuo.The residue is extracted with toluene in a Soxhlet extractor. The crudeproduct is subsequently recrystallized four times from toluene andpurified by sublimation twice in vacuo (p=5×10⁻⁵ mbar, T=290° C.).

Yield: 8.6 g (14 mmol), 36% of theory, purity >99.9% according to HPLC,colourless solid.

Example 2 Synthesis of10-biphenyl-4-yl-2-(4-carbazol-9-ylphenyl)-9,9-dimethyl-9,10-dihydroacridine(HTM3)

10-Biphenyl-4-yl-2-(4-carbazol-9-ylphenyl)-9,9-dimethyl-9,10-dihydro-acridineis prepared analogously to Example 1 starting from9-(4′-bromo-[1,1′-biphenyl]-4-yl)-9H-carbazole (CAS 212385-73-4) andmethyl anthranilate in three steps.

Yield after sublimation: 7.2 g (12 mmol), 37% of theory, purity >99.9%according to HPLC, colourless solid.

Example 3 Synthesis of9,9-diphenyl-10-(9-phenyl-9H-carbazol-3-yl)-9,10-dihydroacridine (H3)

Caesium carbonate (30.6 g, 94 mmol), palladium acetate (0.5 g, 2 mmol)and xantphos (0.9 g, 5 mmol) are added to a solution of9,10-dihydro-9,9-diphenylacridine (CAS 20474-15-1, 15.7 g, 47 mmol) and3-bromo-9-phenyl-9H-carbazole (CAS 1153-85-1, 15.1 g, 47 mmol) indegassed toluene (300 ml), and the mixture is heated under reflux for 8h. The precipitated salts are filtered off, and the mother liquor isevaporated in vacuo. The residue is extracted with toluene in a Soxhletextractor. The crude product is subsequently recrystallized three timesfrom toluene and purified by sublimation twice in vacuo (p=5×10⁻⁵ mbar,T=280° C.).

Yield: 10.5 g (18 mmol), 38% of theory, purity >99.9% according to HPLC,colourless solid.

Example 4 Synthesis of9,9-dimethyl-10-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9,10-dihydroacridine(HTM4)

9,9-Dimethyl-10-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9,10-dihydroacridineis prepared analogously to Example 3 starting from3-(4-bromophenyl)-9-phenyl-9H-carbazole (CAS 1028647-93-9) and9,10-dihydro-9,9-dimethylacridine (CAS 6267-02-3).

Yield after sublimation: 9.6 g (18 mmol), 36% of theory, purity >99.9%according to HPLC, colourless solid.

Example 5 Synthesis of10-[4-(3,6-di-tert-butylcarbazol-9-yl)phenyl]-9,9-dimethyl-9,10-dihydroacridine(H4)

10-[4-(3,6-Di-tert-butylcarbazol-9-yl)phenyl]-9,9-dimethyl-9,10-dihydroacridineis prepared analogously to Example 3 starting from9-(4-bromophenyl)-3,6-bis-tert-butyl-9H-carbazole (CAS 601454-33-5) and9,10-dihydro-9,9-dimethylacridine (CAS 6267-02-3). Yield aftersublimation: 11.2 g (20 mmol), 39% of theory, purity >99.9% according toHPLC, colourless solid.

Example 6 Synthesis of10-(4′-carbazol-9-ylbiphenyl-4-yl)-9,9-diphenyl-9,10-dihydroacridine(H5)

10-(4′-Carbazol-9-ylbiphenyl-4-yl)-9,9-diphenyl-9,10-dihydroacridine isprepared analogously to Example 3 starting from9-(4′-bromo-[1,1′-biphenyl]-4-yl)-9H-carbazole (CAS 212385-73-4) and9,10-dihydro-9,9-diphenylacridine (CAS 20474-15-1).

Yield after sublimation: 8.7 g (13 mmol), 34% of theory, purity >99.9%according to HPLC, colourless solid.

Example 7 Synthesis of5,5,9,9-tetramethyl-3-(9-phenyl-9H-carbazol-3-yl)-5H,9H-13b-azanaphtho[3,2,1-de]anthracene(HTM5)

a) Dimethyl 2-[(4-bromophenyl)phenylamino]isophthalate

N-Bromosuccinimide (35.4 g, 199 mmol) is added in portions to a solutionof dimethyl 2-diphenylaminoisophthalate (CAS 66131-47-3, 80 g, 221 mmol)in chloroform (2000 ml) at 0° C. with exclusion of light, and themixture is stirred at this temperature for 2 h. The reaction isterminated by addition of sodium sulfite solution, and the mixture isstirred at room temperature for a further 30 min. After phaseseparation, the organic phase is washed with water, and the aqueousphase is extracted with dichloromethane. The combined organic phases aredried over sodium sulfate and evaporated in vacuo. The residue isdissolved in ethyl acetate and filtered through silica gel. The crudeproduct is subsequently recrystallized from heptane.

Yield: 57.2 g (129 mmol), 65% of theory, colourless solid.

b) 3-Bromo-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]-anthracene

Dimethyl 2-[(4-bromophenyl)phenylamino]isophthalate (57.0 g, 129 mmol)is added in portions to a suspension of anhydrous cerium(III) chloride(35.0 g, 142 mmol) in dried tetrahydrofuran (800 ml). A 3 M solution ofmethylmagnesium chloride in tetrahydrofuran (129.0 ml, 387 mmol) issubsequently added dropwise at 0° C., and the mixture is stirred at roomtemperature for 20 h. The reaction mixture is neutralized using 25%acetic acid (about 120 ml) with ice-cooling and diluted with dist. waterand ethyl acetate. The aqueous phase is extracted with ethyl acetate,dried over sodium sulfate and evaporated in vacuo.

The residue is dissolved in dichloromethane (200 ml) and added dropwiseover the course of 20 min to a solution of polyphosphoric acid (101.1 g,877 mmol) and methanesulfonic acid (57.5 ml, 877 mmol) indichloromethane (200 ml). The reaction mixture is stirred at roomtemperature for 1 h and subsequently evaporated in vacuo. The residue istaken up in ethyl acetate, washed with dist. water, dried over sodiumsulfate and evaporated in vacuo. The residue is dissolved in ethylacetate and filtered through basic aluminium oxide. The crude product issubsequently recrystallized from ethyl acetate.

Yield: 39.6 g (98 mmol), 76% of theory, colourless solid.

c)5,5,9,9-Tetramethyl-3-(9-phenyl-9H-carbazol-3-yl)-5H,9H-13b-azanaphtho[3,2,1-de]anthracene

(9-Phenyl-9H-carbazol-3-yl)boronic acid (CAS 854952-58-2, 33.0 g, 115mmol),3-bromo-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]-anthracene(39.0 g, 96 mmol) and potassium phosphate monohydrate (66.3 g, 288 mmol)are initially introduced in a mixture of 300 ml of dist. water, 200 mlof toluene and 100 ml of dioxane and saturated with N₂ for 30 min.Tetrakis(triphenylphosphine)palladium (3.3 g, 3 mmol) is subsequentlyadded, and the mixture is heated under reflux for 3 h. After dilutionwith toluene, the organic phase is separated off, washed twice withwater, dried over Na₂SO₄ and evaporated in vacuo. The residue isextracted with toluene in a Soxhlet extractor. The crude product issubsequently recrystallized four times from toluene and purified bysublimation twice in vacuo (p=5×10⁻⁵ mbar, T=290° C.).

Yield: 17.6 g (31 mmol), 32% of theory, purity >99.9% according to HPLC,colourless solid.

Example 8 Synthesis of3-(4-carbazol-9-ylphenyl)-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene(H6)

3-(4-Carbazol-9-ylphenyl)-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho-[3,2,1-de]anthraceneis prepared analogously to Example 7c) starting from3-bromo-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene and[4-(carbazol-9-yl)phenyl]boronic acid (CAS 419536-33-7).

Yield after sublimation: 9.4 g (17 mmol), 37% of theory, purity >99.9%according to HPLC, colourless solid.

Example 9 Synthesis of5,5,9,9-tetramethyl-7-(9-phenyl-9H-carbazol-3-yl)-5H,9H-13b-azanaphtho[3,2,1-de]anthracene(HTM6)

a) 7-Bromo-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]-anthracene

N-Bromosuccinimide (24.7 g, 139 mmol) is added in portions to a solutionof 5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene (CAS52066-62-3, 50 g, 154 mmol) in chloroform (1000 ml) at 0° C. withexclusion of light, and the mixture is stirred at this temperature for 2h. The reaction is terminated by addition of sodium sulfite solution,and the mixture is stirred at room temperature for a further 30 min.After phase separation, the organic phase is washed with water, and theaqueous phase is extracted with dichloromethane. The combined organicphases are dried over sodium sulfate and evaporated in vacuo. Theresidue is dissolved in ethyl acetate and filtered through silica gel.The crude product is subsequently recrystallized from heptane.

Yield: 35.6 g (88 mmol), 63% of theory, colourless solid.

b)5,5,9,9-Tetramethyl-7-(9-phenyl-9H-carbazol-3-yl)-5H,9H-13b-azanaphtho[3,2,1-de]anthracene

(9-Phenyl-9H-carbazol-3-yl)boronic acid (CAS 854952-58-2, 29.9 g, 104mmol),7-bromo-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]-anthracene(35.0 g, 87 mmol) and potassium phosphate monohydrate (60.1 g, 261 mmol)are initially introduced in a mixture of 300 ml of dist. water, 200 mlof toluene and 100 ml of dioxane and saturated with N₂ for 30 min.Tetrakis(triphenylphosphine)palladium (3.0 g, 3 mmol) is subsequentlyadded, and the mixture is heated under reflux for 3 h. After dilutionwith toluene, the organic phase is separated off, washed twice withwater, dried over Na₂SO₄ and evaporated in vacuo. The residue isextracted with toluene in a Soxhlet extractor. The crude product issubsequently recrystallized four times from toluene and purified bysublimation twice in vacuo (p=5×10⁻⁵ mbar, T=290° C.).

Yield: 17.0 g (30 mmol), 34% of theory, purity >99.9% according to HPLC,colourless solid.

Example 10 Synthesis of7-(4-carbazol-9-ylphenyl)-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene(H7)

7-(4-Carbazol-9-ylphenyl)-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho-[3,2,1-de]anthraceneis prepared analogously to Example 9b) starting from7-bromo-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene and[4-(carbazol-9-yl)phenyl]boronic acid (CAS 419536-33-7).

Yield after sublimation: 10.3 g (18 mmol), 34% of theory, purity >99.9%according to HPLC, colourless solid.

Example 11 Synthesis of4,4,8,8,12,12-hexamethyl-2-(9-phenyl-9H-carbazol-3-yl)-4H,8H,12H-12c-azadibenzo[cd,mn]pyrene(HTM7)

(9-Phenyl-9H-carbazol-3-yl)boronic acid (CAS 854952-58-2, 31.0 g, 108mmol),2-bromo-4,4,8,8,12,12-hexamethyl-4H,8H,12H-12c-azadibenzo[cd,mn]pyrene(40.0 g, 90 mmol) and potassium phosphate monohydrate (62.2 g, 270 mmol)are initially introduced in a mixture of 300 ml of dist. water, 200 mlof toluene and 100 ml of dioxane and saturated with N₂ for 30 min.Tetrakis(triphenylphosphine)palladium (3.1 g, 3 mmol) is subsequentlyadded, and the mixture is heated under reflux for 3 h. After dilutionwith toluene, the organic phase is separated off, washed twice withwater, dried over Na₂SO₄ and evaporated in vacuo. The residue isextracted with toluene in a Soxhlet extractor. The crude product issubsequently recrystallized three times from toluene and purified bysublimation twice in vacuo (p=5×10⁻⁵ mbar, T=295° C.).

Yield: 15.8 g (26 mmol), 29% of theory, purity >99.9% according to HPLC,colourless solid.

Example 12 Synthesis of2,6-di-tert-butyl-10-(4-carbazol-9-ylphenyl)-4,4,8,8,12,12-hexamethyl-4H,8H,12H-12c-azadibenzo[cd,mn]pyrene(HTM8)

2,6-Di-tert-butyl-10-(4-carbazol-9-ylphenyl)-4,4,8,8,12,12-hexamethyl-4H,8H,12H-12c-azadibenzo[cd,mn]pyreneis prepared analogously to Example 11 starting from2-bromo-6,10-di-tert-butyl-4,4,8,8,12,12-hexamethyl-4H,8H,12H-12c-azadibenzo[cd,mn]pyrene(CAS 1097721-82-8) and [4-(carbazol-9-yl)phenyl]boronic acid (CAS419536-33-7). Yield after sublimation: 7.8 g (11 mmol), 27% of theory,purity >99.9% according to HPLC, colourless solid.

Example 13 Synthesis of3-(10-biphenyl-4-yl-12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluoren-7-yl)-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene(HTM9)

a)5,5,9,9-Tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene-3-boronicacid

74.5 ml (149 mmol) of a 2 M solution of n-butyllithium in cyclohexaneare slowly added to a solution of3-bromo-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene(Example 7b, 50.0 g, 124 mmol) in dry tetrahydrofuran (600 ml) at −75°C. The reaction mixture is stirred at −75° C. for 1 h, 27.6 ml (248mmol) of trimethyl borate are added, and the mixture is warmed overnightat room temperature. For work-up, the mixture is diluted with ethylacetate/dist. water/glacial acetic acid (6/2/1). The organic phase isseparated off, washed with dist. water and dried over sodium sulfate.The crude product obtained after removal of the solvent in vacuo isemployed in the next step without further purification.

Yield: 39.9 g (108 mmol), 87% of theory, colourless solid.

b)3-(10-Biphenyl-4-yl-12,12-dimethyl-10,12-dihydro-10-azaindeno-[2,1-b]fluoren-7-yl)-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho-[3,2,1-de]anthracene

5,5,9,9-Tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene-3-boronicacid (20.0 g, 54 mmol),10-biphenyl-4-yl-7-bromo-12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene(see as yet unpublished DE 102009023155.2, 23.2 g, 45 mmol) andpotassium phosphate monohydrate (31.1 g, 135 mmol) are initiallyintroduced in a mixture of 150 ml of dist. water, 100 ml of toluene and50 ml of dioxane and saturated with N₂ for 30 min.Tetrakis(triphenylphosphine)palladium (1.6 g, 1 mmol) is subsequentlyadded, and the mixture is heated under reflux for 3 h. After dilutionwith toluene, the organic phase is separated off, washed twice withwater, dried over Na₂SO₄ and evaporated in vacuo. The residue isextracted with toluene in a Soxhlet extractor. The crude product issubsequently recrystallized five times from toluene and purified bysublimation twice in vacuo (p=5×10⁻⁵ mbar, T=320° C.).

Yield: 10.9 g (14 mmol), 32% of theory, purity >99.9% according to HPLC,colourless solid.

Example 14 Synthesis of3-(11,12-diphenyl-11,12-dihydro-11,12-diazaindeno[2,1-a]fluoren-3-yl)-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene(HTM10)

a)3-Bromo-(11,12-diphenyl-11,12-dihydro-11,12-diazaindeno[2,1-a]-fluorene

N-Bromosuccinimide (15.7 g, 88 mmol) is added in portions to a solutionof 11,12-diphenyl-11,12-dihydro-11,12-diazaindeno[2,1-a]fluorene (CAS222044-88-4, 40 g, 98 mmol) in chloroform (800 ml) at 0° C. withexclusion of light, and the mixture is stirred at this temperature for 2h. The reaction is terminated by addition of sodium sulfite solution,and the mixture is stirred at room temperature for a further 30 min.After phase separation, the organic phase is washed with water, and theaqueous phase is extracted with dichloromethane. The combined organicphases are dried over sodium sulfate and evaporated in vacuo. Theresidue is dissolved in ethyl acetate and filtered through silica gel.The crude product is subsequently recrystallized from heptane.

Yield: 28.3 g (58 mmol), 66% of theory, colourless solid.

b)3-(11,12-Diphenyl-11,12-dihydro-11,12-diazaindeno[2,1-a]fluoren-3-yl)-5,5,9,9-tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene

5,5,9,9-Tetramethyl-5H,9H-13b-azanaphtho[3,2,1-de]anthracene-3-boronicacid (Example 13a, 19.0 g, 51 mmol),3-bromo-(11,12-diphenyl-11,12-dihydro-11,12-diazaindeno[2,1-a]fluorene(21.0 g, 43 mmol) and potassium phosphate monohydrate (29.7 g, 129 mmol)are initially introduced in a mixture of 150 ml of dist. water, 100 mlof toluene and 50 ml of dioxane and saturated with N₂ for 30 min.Tetrakis(triphenylphosphine)palladium (1.5 g, 1 mmol) is subsequentlyadded, and the mixture is heated under reflux for 3 h. After dilutionwith toluene, the organic phase is separated off, washed twice withwater, dried over Na₂SO₄ and evaporated in vacuo. The residue isextracted with toluene in a Soxhlet extractor. The crude product issubsequently recrystallized five times from toluene and purified bysublimation twice in vacuo (p=5×10⁻⁵ mbar, T=315° C.). Yield: 9.5 g (13mmol), 30% of theory, purity >99.9% according to HPLC, colourless solid.

Examples 15-26 Syntheses of Compounds Containing Bridging Groups —O— and—S— a) Synthesis of the precursor7-bromo-9,9-dimethyl-9H-quino-[3,2,1-kl]phenothiazine

N-Bromosuccinimide (24.7 g, 139 mmol) is added in portions to a solutionof 9,9-dimethyl-9H-quino[3,2,1-kl]phenothiazine (CAS 73183-70-7, 48.5 g,154 mmol) in chloroform (1000 ml) at 0° C. with exclusion of light, andthe mixture is stirred at this temperature for 2 h. The reaction isterminated by addition of sodium sulfite solution, and the mixture isstirred at room temperature for a further 30 min. After phaseseparation, the organic phase is washed with water, and the aqueousphase is extracted with dichloromethane. The combined organic phases aredried over sodium sulfate and evaporated in vacuo. The residue isdissolved in ethyl acetate and filtered through silica gel. The crudeproduct is subsequently recrystallized from heptane.

Yield: 41.9 g (104 mmol), 69% of theory, colourless solid.

b) Synthesis of the precursor7-bromo-9,9-dimethyl-9H-quino-[3,2,1-kl]phenoxazine

N-Bromosuccinimide (24.7 g, 139 mmol) is added in portions to a solutionof 9,9-dimethyl-9H-quino[3,2,1-kl]phenoxazine (CAS 73183-73-0, 46 g, 154mmol) in chloroform (1000 ml) at 0° C. with exclusion of light, and themixture is stirred at this temperature for 2 h. The reaction isterminated by addition of sodium sulfite solution, and the mixture isstirred at room temperature for a further 30 min. After phaseseparation, the organic phase is washed with water, and the aqueousphase is extracted with dichloromethane. The combined organic phases aredried over sodium sulfate and evaporated in vacuo. The residue isdissolved in ethyl acetate and filtered through silica gel. The crudeproduct is subsequently recrystallized from heptane.

Yield: 37 g (100 mmol), 64% of theory, colourless solid.

c) Synthesis of the precursor7-bromo-1,4-benzothiazino[2,3,4-kl]-phenothiazine

N-Bromosuccinimide (24.7 g, 139 mmol) is added in portions to a solutionof 1,4-benzothiazino[2,3,4-kl]phenothiazine (CAS 1050521-47, 48.5 g, 154mmol) in chloroform (1000 ml) at 0° C. with exclusion of light, and themixture is stirred at this temperature for 2 h. The reaction isterminated by addition of sodium sulfite solution, and the mixture isstirred at room temperature for a further 30 min. After phaseseparation, the organic phase is washed with water, and the aqueousphase is extracted with dichloromethane. The combined organic phases aredried over sodium sulfate and evaporated in vacuo. The residue isdissolved in ethyl acetate and filtered through silica gel. The crudeproduct is subsequently recrystallized from heptane.

Yield: 42 g (110 mmol), 64% of theory, colourless solid.

d) Synthesis of the precursor 7-bromo1,4-benzoxazino[2,3,4-kl]-phenoxazine

N-Bromosuccinimide (24.7 g, 139 mmol) is added in portions to a solutionof 1,4-benzoxazino[2,3,4-kl]phenoxazine (CAS 784189-24-8, 42 g, 154mmol) in chloroform (1000 ml) at 0° C. with exclusion of light, and themixture is stirred at this temperature for 2 h. The reaction isterminated by addition of sodium sulfite solution, and the mixture isstirred at room temperature for a further 30 min. After phaseseparation, the organic phase is washed with water, and the aqueousphase is extracted with dichloromethane. The combined organic phases aredried over sodium sulfate and evaporated in vacuo. The residue isdissolved in ethyl acetate and filtered through silica gel. The crudeproduct is subsequently recrystallized from heptane.

Yield: 31 g (89 mmol), 58% of theory, colourless solid.

e) Synthesis of Compound Examples 15-26 General Procedure for CompoundExample 159,9-Dimethyl-7-(9-phenyl-9H-carbazol-3-yl)-9H-5-thia-13b-azanaphtho-[3,2,1-de]anthracene(HTM12)

(9-Phenyl-9H-carbazol-3-yl)boronic acid (CAS 854952-58-2, 33.0 g, 115mmol), 7-bromo-9,9-dimethyl-9H-quino[3,2,1-kl]phenothiazine (27 g, 96mmol) and potassium phosphate monohydrate (66.3 g, 288 mmol) areinitially introduced in a mixture of 300 ml of dist. water, 200 ml oftoluene and 100 ml of dioxane and saturated with N₂ for 30 min.Tetrakis(triphenylphosphine)palladium (3.3 g, 3 mmol) is subsequentlyadded, and the mixture is heated under reflux for 3 h. After dilutionwith toluene, the organic phase is separated off, washed twice withwater, dried over Na₂SO₄ and evaporated in vacuo. The residue isextracted with toluene in a Soxhlet extractor. The crude product issubsequently recrystallized four times from toluene and purified bysublimation twice in vacuo (p=5×10⁻⁵ mbar, T=290° C.).

Yield: 28 g (50 mmol), 75% of theory, purity >99.9% according to HPLC,colourless solid.

The following compounds are obtained analogously (Examples 16-26):

Starting Starting Ex. material 1 material 2 Product Yield 16 (HTM15)

  419536-33-7

63% 17 (HTM17)

  1001911-63-2

73% 18 (HTM11)

  854952-58-2

79% 19 (HTM16)

  1001911-63-2

70% 20 (H8)

  419536-33-7

74% 21 (HTM14)

  854952-58-2

77% 22 (HTM18)

  1001911-63-2

63% 23 (H9)

  419536-33-7

56% 24 (HTM13)

  854952-58-2

70% 25 (HTM19)

  1001911-63-2

78% 26 (H10)

  419536-33-7

77%

Example 27 Synthesis of9,9-dimethyl-10-phenyl-2,7-bis-(9-phenyl-9H-carbazol-3-yl)-9,10-dihydroacridinea) 2,7-Dibromo-9,9-dimethyl-9,10-dihydroacridine

N-Bromosuccinimide (94.5 g, 531 mmol) is added in portions to a solutionof 9,9-dimethyl-9,10-dihydroacridine (CAS 6267-02-3, 45 g, 252 mmol) inchloroform (1000 ml) at 0° C. with exclusion of light, and the mixtureis stirred at this temperature for 2 h. 500 ml of water are subsequentlyadded to the mixture. After phase separation, the organic phase iswashed with water, and the aqueous phase is extracted with chloroform.The combined organic phases are dried over sodium sulfate and evaporatedin vacuo. The residue is dissolved in ethyl acetate and filtered throughsilica gel. The crude product is subsequently recrystallized fromheptane.

Yield: 64.7 g (176 mmol), 70% of theory, colourless solid.

b) 2,7-Dibromo-9,9-dimethyl-10-phenyl-9,10-dihydroacridine

A degassed solution of 16.6 ml (147 mmol) of 4-iodobenzene and 45.1 g(123 mmol) of 2,7-dibromo-9,9-dimethyl-9,10-dihydroacridine in 600 ml oftoluene is saturated with N₂ for 1 h. Then, firstly 2.09 ml (8.6 mmol)of P(tBu)₃, then 1.38 g (6.1 mmol) of palladium(II) acetate are added tothe solution, and 17.7 g (185 mmol) of NaOtBu in the solid state aresubsequently added. The reaction mixture is heated under reflux for 1 h.After cooling to room temperature, 500 ml of water are carefully added.The aqueous phase is washed with 3×50 ml of toluene, dried over MgSO₄,and the solvent is removed in vacuo. Filtration of the crude productthrough silica gel with heptane/ethyl acetate (20:1) gives 44.1 g (99.6mmol, 81%) of 2,7-dibromo-9,9-dimethyl-10-phenyl-9,10-dihydroacridine aspale-yellow crystals.

c)9,9-Dimethyl-10-phenyl-2,7-bis-(9-phenyl-9H-carbazol-3-yl)-9,10-dihydroacridine

(9-Phenyl-9H-carbazol-3-yl)boronic acid (CAS 854952-58-2, 60.6 g, 211mmol), 2,7-dibromo-9,9-dimethyl-10-phenyl-9,10-dihydroacridine (42.5 g,96 mmol) and potassium phosphate monohydrate (66.3 g, 288 mmol) areinitially introduced in a mixture of 300 ml of dist. water, 200 ml oftoluene and 100 ml of dioxane and saturated with N₂ for 30 min.Tetrakis(triphenylphosphine)palladium (3.3 g, 3 mmol) is subsequentlyadded, and the mixture is heated under reflux for 3 h. After dilutionwith toluene, the organic phase is separated off, washed twice withwater, dried over Na₂SO₄ and evaporated in vacuo. The residue isextracted with toluene in a Soxhlet extractor. The crude product issubsequently recrystallized four times from toluene and purified bysublimation twice in vacuo.

Yield: 21.5 g (50 mmol), 75% of theory, purity >99.9% according to HPLC,colourless solid.

B) DEVICE EXAMPLES

OLEDs according to the invention and OLEDs in accordance with the priorart are produced by a general process in accordance with WO 04/058911,which is adapted to the circumstances described here (layer-thicknessvariation, materials).

The data for various OLEDs are presented in Examples C1 to I44 below(see Tables 1 and 2). Glass plates coated with structured ITO (indiumtin oxide) in a thickness of 150 nm are coated with 20 nm of PEDOT(poly(3,4-ethylenedioxy-2,5-thiophene), applied by spin coating fromwater; purchased from H. C. Starck, Goslar, Germany) for improvedprocessing.

These coated glass plates form the substrates to which the OLEDs areapplied. The OLEDs have basically the following layer structure:substrate/optional hole-injection layer (HIL)/hole-transport layer(HTL)/optional interlayer (IL)/electron-blocking layer (EBL)/emissionlayer (EML)/optional hole-blocking layer (HBL)/electron-transport layer(ETL)/optional electron-injection layer (EIL) and finally a cathode. Thecathode is formed by an aluminium layer with a thickness of 100 nm. Theprecise structure of the OLEDs is shown in Table 1. The materialsemployed for the production of the OLEDs are shown in Table 3.

All materials are applied by thermal vapour deposition in a vacuumchamber. The emission layer here always consists of at least one matrixmaterial (host material) and an emitting dopant (emitter), which isadmixed with the matrix material or materials in a certain proportion byvolume by coevaporation. A specification such as ST1:CBP:TER1(55%:35%:10%) here means that material ST1 is present in the layer in aproportion by volume of 55%, CBP is present in the layer in a proportionof 35% and TER1 is present in the layer in a proportion of 10%.Analogously, the electrontransport layer may also consist of a mixtureof two materials.

The OLEDs are characterised by standard methods. For this purpose, theelectroluminescence spectra, the current efficiency (measured in cd/A),the power efficiency (measured in lm/W) and the external quantumefficiency (EQE, measured in percent) as a function of the luminousdensity, calculated from current/voltage/luminous density characteristiclines (IUL characteristic lines), and the lifetime are determined. Theelectroluminescence spectrum are determined at a luminous density of1000 cd/m², and the CIE 1931 x and y colour coordinates are calculatedtherefrom. The term U1000 in Table 2 denotes the voltage required for aluminous density of 1000 cd/m². CE1000 and PE1000 denote the current andpower efficiencies achieved at 1000 cd/m². Finally, EQE1000 is theexternal quantum efficiency at an operating luminous density of 1000cd/m². The lifetime LT is defined as the time after which the luminousdensity drops from the initial luminous density L0 to a certainproportion L1 on operation at constant current. A specification ofL0=4000 cd/m² and L1=80% in Table 2 means that the lifetime indicated incolumn LT corresponds to the time after which the initial luminousdensity of the corresponding OLED drops from 4000 cd/m² to 3200 cd/m².The values for the lifetime can be converted into a specification forother initial luminous densities with the aid of conversion formulaeknown to the person skilled in the art. The lifetime for an initialluminous density of 1000 cd/m² is a usual specification here.

The data for the various OLEDs are summarized in Table 2. Example C1-C16are comparative examples in accordance with the prior art, ExamplesI1-I44 show data of OLEDs in which materials according to the inventionare employed.

Some of the examples are explained in greater detail below in order toillustrate the advantages of the compounds according to the invention.However, it should be pointed out that this only represents a selectionof the data shown in Table 2. As revealed by the table, significantimprovements over the prior art are also achieved on use of thecompounds according to the invention which are not discussed in detailbelow. In some cases, an improvement in all parameters is achieved, butin some cases only an improvement in either the efficiency or thevoltage or the lifetime is observed. However, even the improvement ofone of the said parameters represents a significant advance, sincedifferent applications require optimization with respect to differentparameters.

Use of Compounds According to the Invention as Hole-Transport orHole-Injection Materials

OLEDs C1-C4 are comparative examples in accordance with the prior art inwhich fluorescent dopants D1-D3 are employed in combination with matrixmaterials H1 and H2, hole-transport materials HTM1, SpNPB, NPB, thecarbazole-substituted planar amine PACbz and electron-transportmaterials Alga, ETM1, ST1 and ST2.

If material HTM1 in accordance with the prior art is replaced bycompound HTM7 according to the invention (Examples I1, I2 and C2, C3),the current efficiency of the OLEDs remains approximately the same,while the operating voltage drops slightly and the lifetime increasessignificantly by up to about 30% (Examples I1, C3). A similarimprovement in the performance data is obtained if HTM7 is employeddirectly as hole-injection layer (Examples I24, C5). In this case, theimprovement in the lifetime is about 40%, and the power efficiency alsoincreases significantly by about 10% due to the significantly reducedoperating voltage.

Significant improvements are likewise obtained on use of compoundsaccording to the invention if these are directly adjacent to theemission layer of a fluorescent OLED (Examples I3-I12, I25, C1-4). Theuse of compounds HTM2 and HTM3 according to the invention is mentionedhere merely by way of example compared with NPB and PACbz (Examples I3,I6-8, C1-4, C15). On replacement of NPB by HTM3 in combination with theamine-free dopant D3, a significant increase in the power efficiency byabout 15% is obtained (Examples I3, C4), and a very significant increasein the lifetime by somewhat more than 50%.

Compared with PACbz, compound HTM3 in combination with dopant D1exhibits an approximately 30% increased lifetime; compared with NPB, theincrease is somewhat greater than 40% (Examples I7, C2, C15).

The compounds according to the invention also exhibit advantages inOLEDs which comprise a phosphorescent emission layer if they areemployed as hole-transport material. This is demonstrated with referenceto OLEDs which comprise compound ST1 as matrix material and thered-phosphorescent compound TER2 or the green-emitting dopant TEG1 asdopant (Examples I13-16, C5, C8, C16).

With compound HTM2 according to the invention, an approximately 20%increased power efficiency is obtained compared with EBM1, for example(Examples I3, C8); with HTM7, the lifetime can be increased verysignificantly by almost 40% (Examples 115, C8).

The use of compounds according to the invention on the hole-transportside of OLEDs thus produces significant improvements with respect tooperating voltage, efficiency and lifetime.

Use of Compounds According to the Invention as Component in Mixed-MatrixSystems

The use of compounds according to the invention as component inmixed-matrix systems is described below. Systems are shown here whichconsist of two matrix materials and one dopant. The compounds inaccordance with the prior art used are the materials CBP, TCTA and FTPh(Examples C6, C7, C9-C14). The materials according to the invention usedare compounds H3-H10 (Examples I17-I27, I29, I30). The compounds ST1,Ke1 and DAP1 are used as the second matrix component.

If, for example, compound H3 according to the invention is used incombination with ketone matrix Ket1, an increase in the lifetime by morethan 50% compared with the prior art is obtained (Examples C9 and I18).Together with ST1 as second matrix component, a very significantimprovement in the power efficiency by more than 25% compared with theprior art can furthermore be achieved (Examples C7, I17). This isattributable, in particular, to the operating voltage, which issignificantly improved by 0.7 V compared with the prior art. As revealedby Table 2, similar improvements can be achieved with other materialsaccording to the invention, including in red-phosphorescent OLEDs.

Significant improvements thus arise compared with mixed-matrixcomponents in accordance with the prior art, especially with respect tovoltage and lifetime. Since the materials according to the invention canbe employed together with very different classes of matrix materials(ST1, Ket1, DAP1), it can be expected that significant improvements canalso be achieved in combination with other classes of matrix materials,such as, for example, indolocarbazoles, dibenzothiophene derivatives,dibenzofuran derivatives or the like.

TABLE 1 Structure of the OLEDs HIL HTL IL EBL EML HBL ETL EIL Ex.Thickness Thickness Thickness Thickness Thickness Thickness ThicknessThickness C1 HIL1 HTM1 — NPB H1:D1 (95%:5%) — Alq₃ LiF 5 nm 140 nm  20nm 30 nm 20 nm 1 nm C2 HIL1 HTM1 — NPB H1:D1 (95%:5%) — ETM1:LiQ(50%:50%) — 5 nm 140 nm  20 nm 30 nm 20 nm C3 HIL1 HTM1 — NPB H2:D2(90%:10%) — Alq₃ LiF 5 nm 110 nm  20 nm 30 nm 20 nm 1 nm C4 HIL1 SpNPB —NPB H2:D3 (98.5%:1.5%) — ST2:LiQ (50%:50%) — 5 nm 40 nm 20 nm 30 nm 20nm C5 — HTM1 — NPB ST1:TER2 (85%:15%) — Alq₃ LiF 20 nm 20 nm 30 nm 20 nm1 nm C6 — HTM1 — NPB ST1:CBP:TER1 ST1 Alq₃ LiF 20 nm 20 nm (45%:45%:10%)30 nm 10 nm 20 nm 1 nm C7 — HTM1 HIL1 EBM1 ST1:CBP:TEG1 ST1 ST1:LiQ(50%:50%) — 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 10 nm 30 nm C8 — HTM1HIL1 EBM1 ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30nm 10 nm 30 nm C9 HIL1 — — EBM1 Ket1:FTPh:TEG1 Ket1 ETM2 LiF 20 nm  20nm (30%:60%:10%) 30 nm 10 nm 20 nm 1 nm C10 HIL1 — — EBM1 Ket1:FTPh:TEG1Ket1 ETM2 LiF 20 nm  20 nm (60%:30%:10%) 30 nm 10 nm 20 nm 1 nm C11 HIL1— — EBM1 Ket1:TCTA:TEG1 Ket1 ETM2 LiF 20 nm  20 nm (60%:30%:10%) 30 nm10 nm 20 nm 1 nm C12 HIL1 — — EBM1 Ket1:CBP:TEG1 Ket1 ETM2 LiF 20 nm  20nm (60%:30%:10%) 30 nm 10 nm 20 nm 1 nm C13 — HTM1 HIL1 EBM1DAP1:CBP:TEG1 — ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm30 nm C14 — HTM1 HIL1 EBM1 ST1:TCTA:TEG1 — ST1:LiQ (50%:50%) — 70 nm 5nm 90 nm (30%:60%:10%) 30 nm 30 nm C15 HIL1 HTM1 — PACbz H1:D1 (95%:5%)— ETM1:LiQ (50%:50%) — 5 nm 140 nm  20 nm 30 nm 20 nm C16 — HTM1 HIL1PACbz ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30 nm10 nm 30 nm I1 HIL1 HTM7 — NPB H2:D2 (90%:10%) — Alq₃ LiF 5 nm 110 nm 20 nm 30 nm 20 nm 1 nm I2 HIL1 HTM7 — NPB H1:D1 (95%:5%) — ETM1:LiQ(50%:50%) — 5 nm 140 nm  20 nm 30 nm 20 nm I3 HIL1 SpNPB — HTM3 H2:D3(98.5%:1.5%) — ST2:LiQ (50%:50%) — 5 nm 40 nm 20 nm 30 nm 20 nm I4 HIL1SpNPB — HTM4 H2:D3 (98.5%:1.5%) — ST2:LiQ (50%:50%) — 5 nm 40 nm 20 nm30 nm 20 nm I5 HIL1 SpNPB — HTM8 H2:D3 (98.5%:1.5%) — ST2:LiQ (50%:50%)— 5 nm 40 nm 20 nm 30 nm 20 nm I6 HIL1 HTM1 — HTM2 H1:D1 (95%:5%) — Alq₃LiF 5 nm 140 nm  20 nm 30 nm 20 nm 1 nm I7 HIL1 HTM1 — HTM2 H1:D1(95%:5%) — ETM1:LiQ (50%:50%) — 5 nm 140 nm  20 nm 30 nm 20 nm I8 HIL1HTM1 — HTM2 H2:D2 (90%:10%) — Alq₃ LiF 5 nm 110 nm  20 nm 30 nm 20 nm 1nm I9 HIL1 HTM1 — HTM5 H1:D1 (95%:5%) — ETM1:LiQ (50%:50%) — 5 nm 140nm  20 nm 30 nm 20 nm I10 HIL1 HTM1 — HTM6 H1:D1 (95%:5%) — ETM1:LiQ(50%:50%) — 5 nm 140 nm  20 nm 30 nm 20 nm I11 HIL1 HTM1 — HTM9 H1:D1(95%:5%) — ETM1:LiQ (50%:50%) — 5 nm 140 nm  20 nm 30 nm 20 nm I12 HIL1HTM1 — HTM7 H1:D1 (95%:5%) — ETM1:LiQ (50%:50%) — 5 nm 140 nm  20 nm 30nm 20 nm I13 — HTM1 HIL1 HTM2 ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) —70 nm 5 nm 20 nm 30 nm 10 nm 30 nm I14 — HTM1 HIL1 HTM5 ST1:TEG1(90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30 nm 10 nm 30 nm I15— HTM1 HIL1 HTM7 ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm20 nm 30 nm 10 nm 30 nm I16 — HTM1 — HTM2 ST1:TER2 (85%:15%) — Alq₃ LiF20 nm 20 nm 30 nm 20 nm 1 nm I17 — HTM1 HIL1 EBM1 ST1:H3:TEG1 ST1ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 10 nm 30 nm I18HIL1 — — EBM1 Ket1:H3:TEG1 Ket1 ETM2 LiF 20 nm  20 nm (30%:60%:10%) 30nm 10 nm 20 nm 1 nm I19 — HTM1 HIL1 EBM1 DAP1:H3:TEG1 — ST1:LiQ(50%:50%) — 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 30 nm I20 — HTM1 HIL1EBM1 ST1:H5:TEG1 ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm (30%:60%:10%)30 nm 10 nm 30 nm I21 HIL1 — — EBM1 Ket1:H7:TEG1 Ket1 ETM2 LiF 20 nm  20nm (30%:60%:10%) 30 nm 10 nm 20 nm 1 nm I22 — HTM1 — NPB ST1:H4:TER1 ST1Alq₃ LiF 20 nm 20 nm (45%:45%:10%) 30 nm 10 nm 20 nm 1 nm I23 — HTM1 —NPB ST1:H6:TER1 ST1 Alq₃ LiF 20 nm 20 nm (45%:45%:10%) 30 nm 10 nm 20 nm1 nm I24 — HTM7 — NPB ST1:TER2 (85%:15%) — Alq₃ LiF 20 nm 20 nm 30 nm 20nm 1 nm I25 HIL1 HTM1 — HTM9 H1:D1 (95%:5%) — ETM1:LiQ (50%:50%) — 5 nm140 nm  20 nm 30 nm 20 nm I26 — HTM1 — NPB ST1:H8:TER1 ST1 Alq₃ LiF 20nm 20 nm (45%:45%:10%) 30 nm 10 nm 20 nm 1 nm I27 — HTM1 HIL1 EBM1ST1:H8:TEG1 ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm10 nm 30 nm I28 HIL1 SpNPB — H8 H2:D3 (98.5%:1.5%) — ST2:LiQ (50%:50%) —5 nm 40 nm 20 nm 30 nm 20 nm I29 — HTM1 — NPB ST1:H9:TER1 ST1 Alq₃ LiF20 nm 20 nm (45%:45%:10%) 30 nm 10 nm 20 nm 1 nm I30 — HTM1 — NPBST1:H10:TER1 ST1 Alq₃ LiF 20 nm 20 nm (45%:45%:10%) 30 nm 10 nm 20 nm 1nm I31 HIL1 HTM1 — HTM11 H1:D1 (95%:5%) — ETM1:LiQ (50%:50%) — 5 nm 140nm  20 nm 30 nm 20 nm I32 HIL1 HTM1 — HTM11 H2:D2 (90%:10%) — Alq₃ LiF 5nm 110 nm  20 nm 30 nm 20 nm 1 nm I33 — HTM1 HIL1 HTM11 ST1:TEG1(90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30 nm 10 nm 30 nm I34— HTM1 HIL1 HTM12 ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm20 nm 30 nm 10 nm 30 nm I35 — HTM1 HIL1 HTM13 ST1:TEG1 (90%:10%) ST1ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30 nm 10 nm 30 nm I36 — HTM1 HIL1HTM14 ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30 nm10 nm 30 nm I37 — HTM1 HIL1 HTM15 ST1:TEG1 (90%:10%) ST1 ST1:LiQ(50%:50%) — 70 nm 5 nm 20 nm 30 nm 10 nm 30 nm I38 — HTM1 HIL1 HTM16ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30 nm 10 nm30 nm I39 — HTM1 HIL1 HTM17 ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) —70 nm 5 nm 20 nm 30 nm 10 nm 30 nm I40 — HTM1 HIL1 HTM18 ST1:TEG1(90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm 20 nm 30 nm 10 nm 30 nm I41— HTM1 HIL1 HTM19 ST1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) — 70 nm 5 nm20 nm 30 nm 10 nm 30 nm I42 HIL1 HTM1 — HTM16 H1:D1 (95%:5%) — ETM1:LiQ(50%:50%) — 5 nm 140 nm  20 nm 30 nm 20 nm I43 HIL1 HTM1 — HTM16 H2:D2(90%:10%) — Alq₃ LiF 5 nm 110 nm  20 nm 30 nm 20 nm 1 nm I44 HIL1 SpNPB— HTM16 H2:D3 (98.5%:1.5%) — ST2:LiQ (50%:50%) — 5 nm 40 nm 20 nm 30 nm20 nm

TABLE 2 Data for the OLEDs U1000 CE1000 PE1000 EQE CIE x/y at L0 LT Ex.(V) (cd/A) (lm/W) 1000 1000 cd/m² (cd/m²) L1 % (h) C1 6.4 5.1 2.5 4.2%0.14/0.15 6000 50 150 C2 4.7 8.1 5.4 6.3% 0.14/0.15 6000 50 145 C3 5.017.1 10.7 5.0% 0.28/0.61 25000 50 480 C4 4.3 9.8 7.1 7.6% 0.14/0.16 600050 210 C5 6.5 9.0 4.3 8.3% 0.66/0.33 1000 50 18000 C6 5.2 8.1 4.9 11.4%0.68/0.32 1000 50 15000 C7 4.4 48 34 13.3% 0.37/0.60 4000 80 450 C8 4.252 39 14.5% 0.36/0.60 4000 80 330 C9 4.3 45 33 12.6% 0.36/0.61 1000 5039000 C10 4.0 46 36 12.8% 0.36/0.61 1000 50 34000 C11 3.9 42 34 11.6%0.35/0.60 1000 50 14000 C12 4.1 44 34 12.3% 0.36/0.61 1000 50 25000 C134.6 47 32 13.2% 0.36/0.60 1000 50 43000 C14 4.2 43 32 12.0% 0.35/0.601000 50 17000 C15 4.8 8.0 5.2 6.2% 0.14/0.15 6000 50 160 C16 4.3 51 3714.2% 0.36/0.60 4000 80 350 I1 4.8 16.7 10.9 4.9% 0.28/0.61 25000 50 615I2 4.5 8.3 5.8 6.5% 0.14/0.15 6000 50 180 I3 4.0 10.5 8.2 8.1% 0.14/0.166000 50 320 I4 4.1 10.2 7.8 7.8% 0.14/0.16 6000 50 305 I5 4.3 9.3 6.87.2% 0.14/0.16 6000 50 270 I6 6.1 5.1 2.6 4.2% 0.14/0.15 6000 50 200 I74.5 7.7 5.4 6.0% 0.14/0.15 6000 50 210 I8 4.8 17.5 11.5 5.1% 0.28/0.6125000 50 655 I9 4.6 8.0 5.5 6.3% 0.14/0.15 6000 50 185 I10 4.6 7.6 5.25.9% 0.14/0.15 6000 50 185 I11 4.6 7.8 5.3 6.1% 0.14/0.15 6000 50 190I12 4.5 8.5 5.9 6.6% 0.14/0.15 6000 50 225 I13 4.2 63 47 17.5% 0.36/0.604000 80 400 I14 4.0 56 44 15.5% 0.36/0.60 4000 80 375 I15 4.1 61 4717.1% 0.36/0.60 4000 80 455 I16 5.8 10.3 5.6 9.5% 0.66/0.33 1000 5029000 I17 3.7 51 43 14.3% 0.37/0.61 4000 80 585 I18 3.6 52 45 14.5%0.36/0.61 1000 50 60000 I19 3.7 46 39 13.0% 0.37/0.60 1000 50 56000 I203.8 52 43 14.5% 0.36/0.61 4000 80 610 I21 3.5 49 44 13.7% 0.36/0.61 100050 57000 I22 4.9 8.8 5.6 12.3% 0.68/0.32 1000 50 18000 I23 4.7 9.1 6.112.7% 0.68/0.32 1000 50 23000 I24 6.1 9.3 4.8 8.6% 0.66/0.33 1000 5026000 I25 4.5 7.5 5.2 6.0% 0.14/0.15 6000 50 175 I26 4.9 8.7 5.6 12.2%0.68/0.32 1000 50 17000 I27 4.4 47 33 12.9% 0.37/0.61 4000 80 490 I284.2 10.7 8.0 8.3% 0.14/0.16 6000 50 215 I29 5.0 8.4 5.3 11.8% 0.68/0.321000 50 17000 I30 5.1 8.5 5.2 12.0% 0.68/0.32 1000 50 21000 I31 4.7 9.56.4 7.4% 0.14/0.15 6000 50 190 I32 4.9 18.5 11.8 5.4% 0.28/0.61 25000 50540 I33 4.2 57 43 15.9% 0.36/0.60 4000 80 390 I34 4.1 55 43 15.4%0.36/0.60 4000 80 310 I35 4.1 57 43 15.8% 0.36/0.60 4000 80 350 I36 4.255 41 15.2% 0.36/0.60 4000 80 300 I37 4.3 56 41 15.6% 0.36/0.60 4000 80290 I38 4.1 52 40 14.4% 0.36/0.60 4000 80 350 I39 4.2 55 41 15.3%0.36/0.61 4000 80 300 I40 4.1 56 42 15.5% 0.36/0.59 4000 80 270 I41 4.358 42 16.0% 0.36/0.60 4000 80 280 I42 4.6 8.8 6.0 6.9% 0.14/0.15 6000 50110 I43 4.8 17.8 11.5 5.2% 0.28/0.61 25000 50 410 I44 4.2 10.1 7.7 7.9%0.14/0.16 6000 50 180

TABLE 3 Structural formulae of the materials

  HIL1

  HTM1 (prior art)

  NPB (prior art)

  EBM1 (prior art)

  Alq₃

  H1

  H2

  D1

  D2

  ETM1

  ST1

  ETM2

  LiQ

  TEG1

  TER1

  TER2

  CBP (prior art)

  Ket1 (prior art)

  TCTA (prior art)

  ST2

  DAP1

  FTPh (prior art)

  D3

  PA3Cbz (prior art)

  SpNPB

  HTM2 (according to the invention)

  HTM3 (according to the invention)

  HTM4 (according to the invention)

  HTM5 (according to the invention)

  HTM6 (according to the invention)

  HTM7 (according to the invention)

  HTM8 (according to the invention)

  HTM9 (according to the invention)

  H3 (according to the invention)

  H4 (according to the invention)

  H5 (according to the invention)

  H6 (according to the invention)

  H7 (according to the invention)

  HTM10 (according to the invention)

  H8 (according to the invention)

  H9 (according to the invention)

  H10 (according to the invention)

  HTM11 (according to the invention)

  HTM12 (according to the invention)

  HTM13 (according to the invention)

  HTM14 (according to the invention)

  HTM15 (according to the invention)

  HTM16 (according to the invention)

  HTM17 (according to the invention)

  HTM18 (according to the invention)

  HTM19 (according to the invention)

1-15. (canceled)
 16. A compound of the formula (1) or (2)

where the following applies to the symbols and indices occurring: W ison each occurrence equal to Z, where a unit comprising two adjacentgroups W may optionally be replaced by a group of the formula (3)

where the group of the formula (3) is arranged in such a way that thebond between the C atoms labelled with * is condensed onto thesix-membered ring of the carbazole derivative; X is a divalent groupselected from the group consisting of C(R)₂, Si(R)₂, NR, PR, P(═O)R, BR,O, S, C═O, C═S, C═NR, S═O and S(═O)₂; Z is selected on each occurrence,identically or differently, from CR and N, or is equal to C if asubstituent is bonded to the group Z; L is on each occurrence,identically or differently, a divalent group selected from the groupconsisting of C(R)₂, Si(R)₂, NR, PR, P(═O)R, BR, O, S, C═O, C═S, C═NR,C═C(R)₂, S═O, S(═O)₂ and CR═CR; R is, identically or differently on eachoccurrence, H, D, F, Cl, Br, I, CHO, N(R¹)₂, C(═O)R¹, P(═O)(R¹)₂,S(═O)R¹, S(═O)₂R¹, CR¹═C(R¹)₂, CN, NO₂, Si(R¹)₃, B(OR¹)₂, OSO₂R¹, OH,COOR¹, CON(R¹)₂, a straight-chain alkyl, alkoxy or thioalkyl grouphaving 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy orthioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl grouphaving 2 to 40 C atoms, each of which is optionally substituted by oneor more radicals R¹, where one or more non-adjacent CH₂ groups isoptionally replaced by —R¹C═CR¹—, —C≡C—, Si(R¹)₂, Ge(R¹)₂, Sn(R¹)₂, C═O,C═S, C═Se, C═NR¹, P(═O)(R¹), SO, SO₂, NR¹, —O—, —S—, —COO— or —CONR¹—and where one or more H atoms is optionally replaced by D, F, Cl, Br, I,CN or NO₂, or an aromatic or heteroaromatic ring system having 5 to 60aromatic ring atoms, which is optionally in each case substituted by oneor more radicals R¹, or an aryloxy or heteroaryloxy group having 5 to 60aromatic ring atoms, which is optionally substituted by one or moreradicals R¹, or a combination of these systems, where two or moreradicals R is optionally linked to one another and optionally form aring; R¹ is, identically or differently on each occurrence, H, D, F, Cl,Br, I, CHO, N(R²)₂, C(═O)R², P(═O)(R²)₂, S(═O)R², S(═O)₂R², CR²═C(R²)₂,CN, NO₂, Si(R²)₃, B(OR²)₂, OSO₂R², OH, COOR², CON(R²)₂, a straight-chainalkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched orcyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms or analkenyl or alkynyl group having 2 to 40 C atoms, each of which isoptionally substituted by one or more radicals R², where one or morenon-adjacent CH₂ groups is optionally replaced by —R²C═CR²—, —C≡C—,Si(R²)₂, Ge(R²)₂, Sn(R²)₂, C═O, C═S, C═Se, C═NR², P(═O)(R²), SO, SO₂,NR², —O—, —S—, —COO— or —CONR²— and where one or more H atoms isoptionally replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic orheteroaromatic ring system having 5 to 60 aromatic ring atoms, whichoptionally in each case is substituted by one or more radicals R², or anaryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, whichis optionally substituted by one or more radicals R², or a combinationof these systems, where two or more radicals R¹ is optionally linked toone another and may form a ring; R² is, identically or differently oneach occurrence, H, D, F or an aliphatic, aromatic and/or heteroaromaticorganic radical having 1 to 20 C atoms, in which, in addition, one ormore H atoms is optionally replaced by D or F; two or more identical ordifferent substituents R² here optionally also be linked to one anotherand may form a ring; i is equal to 0, 1 or 2, where, for i=0, the twogroups which are bonded to the group with the index i are connecteddirectly to one another; j is equal to 0, 1 or 2, where, for j=0, thetwo groups which are bonded to the group with the index j are connecteddirectly to one another; k is equal to 0 or 1, where, for k=0, thenitrogen atom and the aromatic or heteroaromatic ring which are bondedto the group with the index k are connected directly to one another; nis on each occurrence, identically or differently, 0 or 1, where the sumof the values of the indices n can be equal to 1, 2 or 3; and wherefurthermore a maximum of one substituent R may represent a carbazolederivative, and where the following structures are excluded:


17. The compound according to claim 16, wherein Z is equal to CR or isequal to C if a substituent is bonded to the group Z.
 18. The compoundaccording to claim 16, wherein the compound conforms to one of theformulae (4) to (14)

where the symbols and indices occurring are as defined in claim
 16. 19.The compound according to claim 16, wherein k is equal to
 1. 20. Thecompound according to claim 16, wherein L on each occurrence,identically or differently, is C(R)₂, NR, O, S, C═O, C═NR, S═O, S(═O)₂or CR═CR.
 21. The compound according to claim 16, wherein X is C(R)₂,NR, O, S, C═O, C═NR, S═O or S(═O)₂.
 22. The compound according to claim16, wherein R on each occurrence, identically or differently, is H, D,F, CN, Si(R1)₃, N(R1)₂ or a straight-chain alkyl or alkoxy group having1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3to 20 C atoms, each of which is optionally substituted by one or moreradicals R1, where one or more adjacent or nonadjacent CH2 groups isoptionally replaced by —C≡C—, —R1C═CR1—, Si(R1)₂, C═O, C═NR1, —NR1—,—O—, —S—, —COO— or —CONR1—, or an aryl or heteroaryl group having 5 to30 aromatic ring atoms, which may in each case be substituted by one ormore radicals R1, where two or more radicals R is optionally linked toone another and may form a ring.
 23. The compound according to claim 16,wherein a maximum of one radical R represents a carbazole derivative.24. The compound according to claim 16, wherein the compound conforms toone of the formulae (15) to (74)

where the symbols and indices occurring are as defined in claim
 16. 25.An oligomer, polymer or dendrimer comprising one or more compoundsaccording to claim 16, where the bond(s) to the polymer, oligomer ordendrimer is optionally localized at any desired positions substitutedby a radical R in formula (1) or formula (2).
 26. A formulationcomprising at least one compound according to claim 16 and at least onesolvent.
 27. A formulation comprising at least one polymer, oligomer ordendrimer according to claim 25 and at least one solvent.
 28. A processfor the preparation of the compound of the formula (1) or formula (2)according to claim 16, comprising at least one coupling reaction for thelinking of the moiety containing the carbazole group to the moietycontaining the arylamino group.
 29. An organic electroluminescent device(OLED) comprising at least one compound according to claim
 16. 30. Anelectronic device comprising at least one compound according to claim16.
 31. An electronic device comprising at least one polymer, oligomeror dendrimer according to claim
 25. 32. The electronic device accordingto claim 30, wherein the device is an organic integrated circuit (O-IC),an organic field-effect transistor (O-FET), an organic thin-filmtransistor (O-TFT), an organic light-emitting transistor (O-LET), anorganic solar cell (O-SC), an organic optical detector, an organicphotoreceptor, an organic field-quench devices(O-FQD), a light-emittingelectrochemical cell (LEC), an organic laser diode (O-laser) or anorganic electroluminescent device (OLED).
 33. An organicelectroluminescent device which comprises the compound according toclaim 16 is employed as hole-transport material in a hole-transportlayer or hole-injection layer and/or as matrix material in an emittinglayer.